CN113751008B - Carbon-coated nickel oxide nanocomposite and preparation method and application thereof - Google Patents
Carbon-coated nickel oxide nanocomposite and preparation method and application thereof Download PDFInfo
- Publication number
- CN113751008B CN113751008B CN202010503592.4A CN202010503592A CN113751008B CN 113751008 B CN113751008 B CN 113751008B CN 202010503592 A CN202010503592 A CN 202010503592A CN 113751008 B CN113751008 B CN 113751008B
- Authority
- CN
- China
- Prior art keywords
- nanocomposite
- carbon
- nickel
- metal
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 121
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 81
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000001272 nitrous oxide Substances 0.000 claims abstract description 24
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 19
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 19
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 19
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 19
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 210000000633 nuclear envelope Anatomy 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 46
- 229910052760 oxygen Inorganic materials 0.000 claims description 46
- 239000001301 oxygen Substances 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- 239000012298 atmosphere Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 239000012495 reaction gas Substances 0.000 claims description 17
- 230000000694 effects Effects 0.000 claims description 16
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 15
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000012456 homogeneous solution Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000000921 elemental analysis Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001237 Raman spectrum Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 8
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- -1 organic acid salt Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004378 air conditioning Methods 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 38
- 230000003197 catalytic effect Effects 0.000 abstract description 21
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001361 adipic acid Substances 0.000 abstract description 7
- 235000011037 adipic acid Nutrition 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 45
- 239000010408 film Substances 0.000 description 27
- 239000002131 composite material Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 18
- 229910052573 porcelain Inorganic materials 0.000 description 18
- 239000010410 layer Substances 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000005554 pickling Methods 0.000 description 8
- 239000002344 surface layer Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 229910000314 transition metal oxide Inorganic materials 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 238000004846 x-ray emission Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- VTOPPVCNTXIWOA-UHFFFAOYSA-N cyclohexanol;nitric acid Chemical compound O[N+]([O-])=O.OC1CCCCC1 VTOPPVCNTXIWOA-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B01J35/23—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/402—Dinitrogen oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/30—Improvements relating to adipic acid or caprolactam production
Abstract
The invention provides a carbon-coated nickel oxide nanocomposite, a preparation method and application thereof, and the carbon-coated nickel oxide nanocomposite comprises a method for catalyzing and decomposing nitrous oxide by adopting a catalyst containing the nanocomposite. The nanocomposite comprises a nuclear membrane structure with an outer membrane and an inner core, wherein the outer membrane is a graphitized carbon membrane, the inner core comprises nickel oxide nano particles, the nanocomposite further comprises a second metal, the second metal is alkali metal and/or alkaline earth metal, and the molar ratio of the second metal to nickel is 0.01-0.3. The invention can be reflected in further improving the catalytic activity when the nano composite material doped with alkali metal and/or alkaline earth metal is used for catalyzing the decomposition reaction of nitrous oxide, and is helpful for solving the problem of high concentration N generated in the production process of adipic acid factories, nitric acid factories and the like 2 The problem of eliminating O has good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a carbon-coated nickel oxide nanocomposite, and a preparation method and application thereof.
Background
The transition metal oxide has excellent catalytic performance and photo-electromagnetic performance, is a research hot spot in the field of inorganic materials, and has wide application in energy storage materials, catalytic materials, magnetic recording materials and biological medicines. The carbon material has good conductivity, good chemical/electrochemical stability and high structural strength. The carbon material is used for coating the nano particles of the active metal or the metal oxide, so that the conductivity and the stability of the nano material can be effectively improved, and the nano particles are not easy to agglomerate due to the limited domain effect of the nano particles. In recent years, the carbon-coated nano material is widely applied to the fields of electrocatalysis, super capacitor materials, lithium ion battery anode materials, bioengineering and the like, and also has good application prospects in the field of catalytic science, and particularly, the carbon-coated metal nano material has excellent catalytic activity in oxidation, reduction and other reactions. Amorphous carbon coated transition metal oxide composites are provided in the prior art, but the performance of such materials for catalytic chemical reactions is still greatly lacking.
Nitrous oxide (N) 2 O) is an important temperatureRoom gas, the Global Warming Potential (GWP) of which is CO 2 310 times of CH 4 21 times of (2); in addition, N 2 The average life of O in the atmosphere is about 150 years, also the NO in the stratosphere x The main source of the composition is not only capable of seriously destroying the ozone layer, but also has strong greenhouse effect.
The domestic adipic acid production mainly adopts a cyclohexanol nitric acid oxidation method, and the cyclohexanol is subjected to nitric acid oxidation to produce adipic acid, the technology of the method is mature, the product yield and purity are relatively high, but the nitric acid consumption is large, and a large amount of N is produced in the reaction process 2 O, and the tail gas discharged in the production process is concentrated, the wave quantity is large, and the concentration is high (36-40V%). At present, 15 ten thousand tons of adipic acid and N are produced annually by adopting a cyclohexanol nitric acid oxidation method 2 The annual discharge of O can reach 4.5 ten thousand tons. Therefore, the tail gas of the adipic acid purifying device can effectively control and eliminate N 2 O has become a research hotspot in the field of environmental catalysis today.
The direct catalytic decomposition method can decompose N 2 O is decomposed into nitrogen and oxygen to eliminate N 2 O is the most effective and clean technique. Wherein, the catalyst is the technical core of the direct catalytic decomposition method. Decomposition N reported in the current study 2 The catalyst of O mainly comprises a noble metal catalyst, an ion-exchange molecular sieve catalyst and a transition metal oxide catalyst. Noble metal catalysts (e.g., rh and Ru) on N 2 The O catalytic decomposition has higher low-temperature catalytic activity (the temperature is 250-350 ℃ and N can be efficiently decomposed) 2 O), but it is expensive. Molecular sieve-type catalysts and transition metal oxide catalysts are significantly less expensive than noble metals, but currently these two types of catalysts are relatively more expensive than noble metals for N 2 The activity of O catalytic decomposition is low, and the high-efficiency decomposition temperature is 450-550 ℃. Therefore, the catalyst pair N with low development cost and high activity 2 The emission reduction of O has important significance.
In view of this, there is a very urgent need and broad research prospect to develop new catalytic materials with low cost and high efficiency.
It is noted that the information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
It is a primary object of the present invention to overcome at least one of the above-mentioned drawbacks of the prior art and to provide an alkali metal and/or alkaline earth metal doped carbon-coated nickel oxide nanocomposite comprising a nuclear membrane structure having a graphitized carbon membrane and a nickel oxide core, which has excellent activity as a catalyst active component, particularly excellent effect on the catalytic decomposition of nitrous oxide after doping with alkali metal and/or alkaline earth metal, which helps to solve the high concentration of N generated in the production process of adipic acid plants and nitric acid plants, and a method for preparing the same 2 The elimination of O waste gas has important significance for protecting environment and reducing atmospheric pollution, and has good industrial application prospect.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a carbon-coated nickel oxide nanocomposite, which comprises a nuclear membrane structure with an outer membrane and an inner core, wherein the outer membrane is a graphitized carbon membrane, the inner core comprises nickel oxide nano particles, the nanocomposite further comprises a second metal, the second metal is alkali metal and/or alkaline earth metal, and the molar ratio of the second metal to nickel is 0.01-0.3.
According to one embodiment of the invention, the carbon content is no more than 5wt% of the nanocomposite.
According to one embodiment of the invention, the carbon content is comprised between 0.1% and 5% by weight, preferably between 0.1% and 1% by weight, of the nanocomposite.
According to one embodiment of the invention, the inner core consists of nickel oxide.
According to one embodiment of the present invention, the ratio of the carbon element determined by the X-ray photoelectron spectroscopy to the carbon element content determined by elemental analysis in the nanocomposite is not less than 10 in terms of mass ratio.
According to one embodiment of the invention, the Raman spectrum of the nanocomposite is at 1580cm -1 Near G peak intensity and at 1320cm -1 The ratio of nearby D peak intensities is greater than 2.
According to one embodiment of the invention, the particle size of the nuclear membrane structure is between 1nm and 100nm.
The invention also provides a preparation method of the carbon-coated nickel oxide nanocomposite, which comprises the following steps: placing a nickel source and a polybasic organic carboxylic acid in a solvent, mixing to form a homogeneous solution, and removing the solvent in the homogeneous solution to obtain a precursor; pyrolyzing the precursor in an inert atmosphere or a reducing atmosphere, and carrying out oxygen treatment on a pyrolyzed product; preparing a second metal salt solution, uniformly mixing the product after oxygen treatment with the second metal salt solution, and stirring to obtain a solid-liquid mixture; and (3) drying and roasting the solid-liquid mixture to obtain the nanocomposite.
According to one embodiment of the invention, the acid washing treatment is carried out on the pyrolyzed product before the oxygen treatment.
According to one embodiment of the invention, the acid washing loss rate of the product after the acid washing treatment is less than or equal to 40%, can be less than or equal to 30%, can be less than or equal to 20%, and can be less than or equal to 10%.
According to one embodiment of the invention, the mass ratio of the nickel source to the polybasic organic carboxylic acid is 1 (0.1-10); the nickel source is selected from one or more of organic acid salt of nickel, nickel carbonate, basic nickel carbonate, nickel hydroxide and nickel oxide; the polybasic organic carboxylic acid is selected from one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, gluconic acid and malic acid.
According to one embodiment of the invention, pyrolysis comprises: heating the precursor to a constant temperature section in an inert atmosphere or a reducing atmosphere, and keeping the constant temperature in the constant temperature section; wherein the heating rate is 0.5-10 ℃/min, the constant temperature section temperature is 400-800 ℃, the constant temperature time is 20-600 min, the inert atmosphere is nitrogen or argon, and the reducing atmosphere is the mixed gas of inert gas and hydrogen.
According to one embodiment of the invention, the oxygen treatment comprises introducing a standard gas into the pyrolyzed product and heating, wherein the standard gas contains oxygen and balance gas, and the volume concentration of the oxygen is 10% -40%.
According to one embodiment of the present invention, the temperature of the oxygen treatment is 200 to 500 ℃ and the time of the oxygen treatment is 0.5 to 10 hours.
According to one embodiment of the invention, the second metal salt solution is selected from one or more of an organic acid salt solution of an alkali metal and/or an alkaline earth metal, a carbonate solution, a basic carbonate solution, a nitrate solution and a sulfate solution.
According to one embodiment of the invention, the drying temperature is 60-100 ℃ and the drying time is 15-25 hours; the roasting comprises the following steps: heating the dried product to a constant temperature section, and keeping the constant temperature in the constant temperature section; wherein the heating rate is 0.5-30 ℃/min, the temperature of the constant temperature section is 200-400 ℃, and the constant temperature time is 20-600 min.
The invention also provides application of the nanocomposite as a catalyst active component in catalytic chemical reaction.
The invention also provides a method for catalyzing the decomposition of nitrous oxide, which comprises the step of enabling a catalyst to be in contact with nitrous oxide for catalyzing the decomposition reaction to generate nitrogen and oxygen, wherein the catalyst contains the nanocomposite.
According to one embodiment of the invention, the volume concentration of nitrous oxide in the catalytic decomposition reaction is between 5% and 40%.
According to one embodiment of the invention, in the catalytic decomposition reaction, the reaction temperature is 300-400 ℃, the reaction space velocity is 1000-3000 ml of reaction gas/(hour-gram of nano composite material), and the volume concentration of nitrous oxide in the reaction gas is 30-40%.
According to the technical scheme, the beneficial effects of the invention are as follows:
the carbon-coated nickel oxide nanocomposite material comprises a nuclear membrane structure with a graphitized carbon membrane and a nickel oxide core, and is doped with a second metal, namely an alkali metal and/or an alkaline earth metal. The invention firstly forms a graphitized carbon film tightly coated on the outside by utilizing the action of the transition metal simple substance, and then converts the transition metal simple substance into the transition metal by oxygen treatment And (3) oxide and simultaneously removing amorphous carbon, so that a small amount of graphite carbon tightly coats the nano composite material of the transition metal oxide. The present invention has found that this unique structure and composition allows it to catalyze N as a catalyst active component 2 The O has excellent activity in the decomposition reaction. The invention also discovers that alkali metal and alkaline earth metal can generate a power supply effect, and the alkali metal and alkaline earth metal are doped into the catalyst to play a role of an electronic auxiliary agent, so that the wave mesh and the intensity of an acid position in the catalyst are regulated, and a better catalytic effect is obtained. Compared with the existing catalyst, the N in the industrial waste gas must be reduced 2 O is diluted and then treated, the catalyst can directly catalyze and decompose high-concentration nitrous oxide waste gas generated in industrial production at a lower temperature, the decomposition rate can reach more than 99%, and the catalyst has great significance in protecting environment and reducing atmospheric pollution and has good industrial application prospect.
Drawings
The following drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain the invention, without limitation to the invention.
FIG. 1 is an X-ray diffraction chart of the product obtained in the step (3) of example 1;
FIG. 2 is a transmission electron micrograph of the product obtained in step (3) of example 1;
FIG. 3 is a Raman spectrum of the product obtained in the step (3) of example 1;
FIG. 4 is an X-ray diffraction chart of the product obtained in the step (3) of example 2;
FIG. 5 is a transmission electron micrograph of the product obtained in step (3) of example 2;
FIG. 6 is a Raman spectrum of the product obtained in the step (3) of example 2;
FIG. 7 is an X-ray diffraction chart of the material obtained in comparative example 3;
fig. 8a and 8b are transmission electron microscope images of the material obtained in comparative example 3 at different magnification waves, respectively.
Detailed Description
The following provides various embodiments or examples to enable those skilled in the art to practice the invention as described herein. These are, of course, merely examples and are not intended to limit the invention from that described. The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For a range of wave values, one or more new ranges of wave values may be obtained in combination with each other between the endpoints of each range, between the endpoints of each range and the individual point values, and between the individual point values, and these ranges of wave values should be considered as specifically disclosed herein.
The term "nuclear membrane structure" in the present invention refers to a nuclear membrane structure having an outer membrane, which is a graphitized carbon membrane, and an inner core comprising nickel oxide nanoparticles. The composite material formed by coating the graphitized carbon film with the nickel oxide nano particles is spherical or spheroidic.
The term "graphitized carbon film" refers to a thin film structure composed mainly of graphitized carbon.
The term "carbon element content determined by X-ray photoelectron spectroscopy" refers to the relative content of carbon elements on the surface of a material, which is measured by performing element quantitative analysis by using an X-ray photoelectron spectrometer as an analysis tool.
The term "carbon element content determined in elemental analysis" refers to the relative content of total carbon elements of a material as measured by elemental quantitative analysis using an elemental analyzer as an analysis tool.
The invention provides a carbon-coated nickel oxide nanocomposite, which comprises a nuclear membrane structure with an outer membrane and an inner core, wherein the outer membrane is a graphitized carbon membrane, and the inner core comprises nickel oxide nano particles, and further comprises a second metal, wherein the second metal is alkali metal and/or alkaline earth metal, and the molar ratio of the second metal to the nickel is 0.01-0.3, preferably 0.01-0.2, such as 0.01, 0.05, 0.08, 0.1, 0.13, 0.15, 0.17, 0.18, 0.2 and the like.
According to the present invention, the carbon-coated nickel oxide nanocomposite is a nuclear membrane structure comprising an outer membrane layer and an inner core layer, wherein the outer membrane is mainly composed of a graphitized carbon film, which is mainly composed ofThe graphitized carbon is coated on the surface of the nickel oxide nano particles. In addition, the nanocomposite is further doped with a second metal, i.e., an alkali metal and/or an alkaline earth metal. The inventor of the invention surprisingly found that, although the carbon content of the film layer is relatively small, the nuclear film structure with the graphitized carbon film coated on the outer layer has greatly improved performance, especially catalytic performance, of the whole material, and particularly, the nuclear film structure can not only generate a certain limiting effect, effectively avoid the large aggregation length of nickel oxide nano particles in the inner core, so that the catalytic activity of the composite material is stable, but also synergistically increase the catalytic activity of the whole composite material, and compared with the catalytic activity of pure nickel oxide without the graphitized carbon film, the catalytic activity of the composite material is obviously improved. Furthermore, the nanocomposite is further doped with alkali metal and/or alkaline earth metal, which serves as a catalyst for catalyzing N 2 The reaction of the acidic oxide such as O may be further improved in catalytic activity.
In some embodiments, the aforementioned nanocomposite comprises no more than 5wt% carbon, alternatively no more than 1wt%, such as 1wt%, 0.8wt%, 0.5wt%, 0.3wt%, 0.2wt%, 0.1wt%, etc. of the nanocomposite.
In some embodiments, the ratio of elemental carbon determined by X-ray photoelectron spectroscopy to elemental carbon content determined by elemental analysis in the nanocomposite of the invention is not less than 10. As described above, the carbon element content determined by the X-ray photoelectron spectroscopy refers to the relative content of carbon element on the surface of the material measured by performing elemental quantitative analysis using the X-ray photoelectron spectrometer as an analysis tool. The carbon element content determined in the elemental analysis refers to the relative content of the total carbon element of the material measured by elemental quantitative analysis using an elemental analyzer as an analysis tool. When the ratio of the carbon element determined by the X-ray photoelectron spectroscopy to the carbon element content determined by the elemental analysis is larger, the fact that most of carbon is concentrated on the surface of the material in the whole nano composite material is shown, a carbon film layer is formed, and the nuclear film structure is further formed.
In some embodiments, the nanocomposites of the present invention Raman spectrum of the composite material is at 1580cm -1 G peak intensity in the vicinity and at 1320cm -1 The ratio of nearby D peak intensities is greater than 2. As known to those skilled in the art, the D peak and the G peak are Raman characteristic peaks of C atom crystals, the D peak represents a defect of a carbon atom lattice, and the G peak represents a C atom sp 2 Hybrid in-plane stretching vibration. It is understood that a greater ratio of G-peak intensity to D-peak intensity indicates that more graphitic carbon is present in the nanocomposite than amorphous carbon. That is, the carbon element in the nanocomposite of the present invention exists mainly in the form of graphitic carbon. The graphite carbon has better oxidation resistance, and can synergistically increase catalytic activity with nickel oxide nano particles of the inner core, thereby improving the performance of the whole composite material.
In some embodiments, the particle size of the aforementioned core membrane structures is generally in the range of 1nm to 100nm, preferably 2nm to 40nm, such as 2nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, and the like.
The second aspect of the present invention also provides a method for preparing the aforementioned carbon-coated nickel oxide nanocomposite, comprising the steps of:
placing a nickel source and a polybasic organic carboxylic acid in a solvent, mixing to form a homogeneous solution, and removing the solvent in the homogeneous solution to obtain a precursor; pyrolyzing the precursor in an inert atmosphere or a reducing atmosphere, and carrying out oxygen treatment on a pyrolyzed product; preparing a second metal salt solution, uniformly mixing the product after oxygen treatment with the second metal salt solution, and stirring to obtain a solid-liquid mixture; and drying and roasting the solid-liquid mixture to obtain the nanocomposite.
Specifically, the precursor is a water-soluble mixture, which is obtained by dissolving a nickel source and a polybasic organic carboxylic acid in a solvent such as water, ethanol and the like to form a homogeneous solution, and then directly evaporating the solution to remove the solvent. The aforementioned temperature and process of evaporating the solvent may be any available prior art technique, for example, spray drying at 80-120 ℃, or drying in an oven.
In addition, other organic compounds than the two above may be added together to form a homogeneous solution, and the other organic compounds may be any organic compound that can supplement the carbon source required in the product and that does not contain other doping atoms. Organic compounds which are not volatile, such as organic polyols, lactic acid, etc., are preferred.
In some embodiments, the mass ratio of nickel source, polybasic organic carboxylic acid and other organic compounds is 1:0.1 to 10:0 to 10, preferably 1:0.5 to 5:0 to 5, more preferably 1:0.8 to 3:0 to 3; the nickel source is one or more of organic acid salt of nickel, nickel carbonate, basic nickel carbonate, nickel hydroxide and nickel oxide; preferably, the organic acid salt is a nickel organic carboxylic acid salt containing no other heteroatoms. The polybasic organic carboxylic acid is selected from one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, gluconic acid and malic acid.
In some embodiments, the pyrolyzing comprises: heating the precursor to a constant temperature section in an inert atmosphere or a reducing atmosphere, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-10 ℃ per minute, preferably 2.5-10 ℃ per minute, such as 2.5, 4.5, 5, 6.5, 7, 8.5, 9, 10, etc.; the constant temperature section temperature is 400-800 ℃, preferably 500-700 ℃, such as 500 ℃, 550 ℃, 570 ℃, 610 ℃, 660 ℃, 680 ℃, and the like; the constant temperature is maintained for 20 min-600 min, preferably 30 min-300 min, such as 30min, 45min, 55min, 70min, 86min, 97min, 100min, 180min, 270min, 300min, etc.; the inert atmosphere is nitrogen or argon, the reducing atmosphere is a mixed gas of inert gas and hydrogen, for example, a small amount of hydrogen is doped in the inert atmosphere.
In some embodiments, the invention further comprises subjecting the aforementioned pyrolyzed product to an acid wash treatment.
In fact, the product obtained after the pyrolysis is a nanocomposite material with a graphitized carbon layer coated with nickel. Wherein the "graphitized carbon layer" refers to a carbon structure in which a layered structure is clearly observed under a high resolution transmission electron microscope, not an amorphous structure, and the interlayer spacing is about 0.34nm. The nano composite material with the graphitized carbon layer coated with nickel is a composite material composed of nickel nano particles tightly coated with the graphitized carbon layer (not in contact with the outside), nickel nano particles capable of being in contact with the outside and limited in domain and a carbon material with a mesoporous structure. After pickling treatment, nickel in the composite material has a certain loss, and can be characterized by a pickling loss rate. That is, "pickling loss" refers to the loss ratio of nickel after pickling of the finished carbon-coated nickel nanocomposite product. Reflecting how tightly the graphitized carbon layer coats the nickel. If the graphitized carbon layer does not cover the nickel tightly, the nickel of the inner core is dissolved by the acid after the acid treatment and is lost. The higher the acid washing loss rate, the lower the tightness degree of the graphitized carbon layer on the nickel coating is, and the lower the acid washing loss rate is, the higher the tightness degree of the graphitized carbon layer on the nickel coating is.
In general, specific conditions for the acid washing treatment are: 1g of the sample was added in a proportion of 20mL of an aqueous sulfuric acid solution (1 mol/L), the sample was treated at 90℃for 8 hours, then washed with deionized water to neutrality, dried, weighed, analyzed, and the acid washing loss rate was calculated as follows.
The calculation formula is as follows: the pickling loss rate= [1- (mass wavelet of nickel in the composite after pickling×mass of the composite after pickling)/(mass wavelet of nickel in the composite to be treated×mass of the composite to be treated) ]×100%. It should be noted that the "composite" in this formula is a composite that has not been treated with oxygen. In some embodiments, the composite material generally has a pickling loss of 40% or less, may be 30% or less, may be 20% or less, and may be 10% or less.
The oxygen treatment comprises introducing standard gas into the pyrolyzed or acid-washed product and heating, wherein the standard gas contains oxygen and balance gas, and the volume concentration of the oxygen is 10% -40%, such as 10%, 12%, 15%, 17%, 20%, 22%, 25%, 28% and 30%. The balance gas may be an inert gas such as nitrogen or argon, but the present invention is not limited thereto. In some embodiments, the temperature of the oxygen treatment is 200 ℃ to 500 ℃, preferably 300 ℃ to 400 ℃, such as 320 ℃, 340 ℃, 350 ℃, 380 ℃, etc.; the oxygen treatment time is 0.5 to 10 hours, for example, 1 hour, 3 hours, 5 hours, 7 hours, 8 hours, 10 hours, etc.
Those skilled in the art will recognize that carbon undergoes oxidation reaction to form a gas after contact with oxygen at high temperature, and it is understood that the pyrolyzed precursor forms a nanocomposite material having a graphitized carbon shell coating the nickel core, wherein the carbon content is about 15% to 60%. After the product is subjected to oxygen treatment, amorphous carbon in the material is lost along with the oxidation reaction. However, the inventors of the present invention have unexpectedly found that the oxygen treated material burns off most of the carbon while not only oxidizing the nickel of the core, but also leaving a small portion of the carbon. As described above, the XPS and Raman spectrum detection analysis prove that the part of carbon is a graphitized carbon film layer coated on the surface of nickel oxide, and the film carbon layer further has a plurality of excellent properties, so that the nanocomposite has great application potential in catalytic materials, energy storage materials and electromagnetic materials.
According to the invention, the oxygen treated product is a graphitized carbon film coated nickel oxide nanocomposite material comprising a nuclear film structure having an outer film and an inner core, the outer film being a graphitized carbon film and the inner core comprising nickel oxide nanoparticles. Further, the invention also comprises the steps of uniformly mixing the product after oxygen treatment with the second metal salt solution, stirring for 1-4 hours, fully mixing and contacting the solid and the liquid to obtain a solid-liquid mixture, removing the solvent in the solid-liquid mixture by a drying method and the like, and finally obtaining the carbon-coated nickel oxide nanocomposite doped with alkali metal and/or alkaline earth metal by roasting treatment. It will be appreciated that since the doping process is after the formation of the nuclear membrane structure, the alkali metal and/or alkaline earth metal should be formed on the surface of the nuclear membrane structure.
The solvent of the second metal salt solution is water, and the second metal salt solution is one or more selected from an organic acid salt solution, a carbonate solution, a basic carbonate solution, a nitrate solution and a sulfate solution of alkali metal and/or alkaline earth metal, preferably, a potassium nitrate solution or a potassium carbonate solution.
After being stirred and mixed uniformly, the obtained solid-liquid mixture is dried and roasted. Wherein the drying temperature is 60 to 100 ℃, for example 60 ℃, 65 ℃, 70 ℃, 73 ℃, 77 ℃, 82 ℃, 88 ℃, 90 ℃, 95 ℃, 100 ℃ and the like, and the drying time is 15 to 25 hours, for example 15 hours, 18 hours, 20 hours, 22 hours, 25 hours and the like. The roasting comprises the following steps: heating the dried product to a constant temperature section, and keeping the constant temperature in the constant temperature section; wherein the heating rate is 0.5-30 deg.C/min, preferably 1-10 deg.C/min, such as 1 deg.C/min, 3 deg.C/min, 5 deg.C/min, 6 deg.C/min, 8 deg.C/min, 9 deg.C/min, 10 deg.C/min, etc. The constant temperature is 200-400deg.C, preferably 250-350deg.C, such as 250deg.C, 260deg.C, 300deg.C, 310 deg.C, 320 deg.C, and 350deg.C, and the constant temperature is 20-600 min, preferably 60-480 min, such as 60min, 75min, 88min, 100min, 150min, 166min, 235min, 260min, 350min, 400min, 450min, etc.
In summary, the invention obtains the novel nanocomposite with unique structure and composition by further doping alkali metal and/or alkaline earth metal on the basis of the graphitized carbon film coated nickel oxide nanocomposite. The nanocomposite can be used as a catalyst active component, in particular for catalyzing N 2 The reaction of the acidic oxide such as O may be further improved in catalytic activity.
Specifically, the invention provides a method for decomposing nitrous oxide, which comprises the step of enabling a catalyst to be in contact with the nitrous oxide for catalytic decomposition reaction to generate nitrogen and oxygen, wherein the catalyst contains the nanocomposite. Specifically, a gas containing nitrous oxide is introduced into a reactor containing the catalyst to perform a catalytic decomposition reaction.
In some embodiments, the catalytic decomposition reaction is at a temperature of 300 ℃ to 400 ℃, preferably 350 ℃ to 380 ℃. The space velocity of the catalytic decomposition reaction is 1000-3000 ml of reaction gas/(hour gram of nano composite material). The high reaction space velocity allowed by the invention indicates that the catalyst has high activity and high device processing capacity when the reaction is applied.
According to the invention, as previously described, the decomposition N reported in the current research 2 The catalyst of O mainly comprises noble metal catalystA catalyst, an ion-exchanged molecular sieve-based catalyst, and a transition metal oxide catalyst. Noble metal catalysts, although having a low decomposition temperature, are expensive; the high-efficiency decomposition temperature of other molecular sieve catalysts and transition metal oxide catalysts is 450-550 ℃, and the high temperature required by the reaction greatly improves the industrial cost; in addition, the agglomeration of metal active sites under high temperature conditions also more readily affects the catalytic performance of these catalysts.
The inventors of the present invention have found that the catalyst using the carbon-coated nickel oxide nanocomposite material doped with an alkali metal and/or an alkaline earth metal according to the present invention can effectively decompose nitrous oxide into nitrogen and oxygen, and exhibits excellent stability of catalytic activity in the reaction. In addition, when the existing catalyst is used for catalyzing and decomposing nitrous oxide, the high-concentration nitrous oxide obtained in industrial production is generally required to be diluted to about 0.5% -2%, and the catalyst can be directly decomposed to reach a high decomposition rate without dilution. Namely, the volume concentration of the nitrous oxide is 30% -40%, the catalytic decomposition reaction can be carried out, and the decomposition rate can reach more than 99%, so that the industrial cost is greatly reduced, and the method has good industrial application prospect.
The invention will be further illustrated by the following examples, but the invention is not limited thereby. Unless otherwise indicated, all reagents used in the present invention were analytically pure.
The invention detects the elements on the surface of the material by an X-ray photoelectron spectroscopy (XPS). The X-ray photoelectron spectroscopy analyzer used was an ESCALab220i-XL type radiation electron spectroscopy manufactured by VG scientific company and equipped with Avantage V5.926 software, and the X-ray photoelectron spectroscopy analysis test conditions were: the excitation source is monochromized A1K alpha X-ray with power of 330W and basic vacuum of 3X 10 during analysis and test -9 mbar。
Analysis of carbon (C) was performed on a Elementar Micro Cube elemental analyzer, which was used mainly for analysis of four elements, carbon (C), hydrogen (H), oxygen (O), and nitrogen (N), with the following specific methods and conditions: 1 mg-2 mg of sample is weighed in a tin cup, is put into an automatic sample feeding disc, enters a combustion tube through a ball valve for combustion, the combustion temperature is 1000 ℃ (in order to remove atmospheric interference during sample feeding, helium is adopted for blowing), and then reduction copper is used for reducing the burnt gas to form nitrogen, carbon dioxide and water. The mixed gas is separated by three desorption columns and sequentially enters a TCD detector for detection. The analysis of oxygen element is to convert oxygen in the sample into CO by pyrolysis under the action of a carbon catalyst, and then detect the CO by TCD. Since the composite material of the present invention contains only carbon and metal oxide, the total content of metal oxide can be known from the content of carbon element.
The ratio between the different metal oxides was determined by X-ray fluorescence spectroscopy (XRF) and the content of the different metal oxides in the composite was calculated from the known carbon content. The model of the X-ray fluorescence spectrum analyzer (XRF) adopted by the invention is Rigaku 3013X-ray fluorescence spectrum analyzer, and the X-ray fluorescence spectrum analysis test conditions are as follows: the scan time was 100s and the atmosphere was air.
The Raman detection of the invention adopts a LabRAM HR UV-NIR laser confocal Raman spectrometer manufactured by HORIBA company of Japan, and the laser wavelength is 325nm.
The model of the high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100 (HRTEM) (Japanese electronics Co., ltd.) and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200kV.
The model of the XRD diffractometer adopted by the invention is XRD-6000 type X-ray powder diffractometer (Shimadzu), and XRD testing conditions are as follows: cu target, ka radiation (wavelength λ=0.154 nm), tube voltage 40kV, tube current 200mA, scan speed 10 ° (2θ)/min.
Example 1
This example is used to illustrate the method of preparing the carbon-coated nickel oxide nanocomposite of the present invention.
(1) 10g of nickel carbonate and 10g of citric acid are weighed into a beaker containing 100mL of deionized water, stirred at 70 ℃ to obtain a homogeneous solution, and continuously heated and evaporated to dryness to obtain a solid precursor.
(2) And (3) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow of 100mL/min, heating to 600 ℃ at the speed of 4 ℃/min, stopping heating after keeping the temperature for 2 hours, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel composite material.
(3) And (3) placing the product obtained in the step (2) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing standard gas (the volume concentration of oxygen is 15 percent and nitrogen is balance gas) with the flow rate of 100mL/min, heating to 350 ℃ at the speed of 2 ℃/min, keeping the temperature for 8 hours, stopping heating, and cooling to room temperature under the atmosphere of the standard gas to obtain the graphitized carbon film-coated nickel oxide nanocomposite.
(4) 50ml of deionized water was added to 0.1 g (potassium ca. 0.0014 mol) K 2 CO 3 A solution was prepared and 8.5g of the product from step (3) (about 0.14mol of nickel) was added to K 2 CO 3 The solution is evenly mixed and stirred, and after 4 hours; and (3) placing the obtained solid-liquid mixture in an oven at 80 ℃, drying for 12 hours, then placing in a tube furnace, introducing nitrogen, heating to 350 ℃ at a speed of 5 ℃/min, keeping the temperature for 4 hours, stopping heating, and cooling to room temperature under the nitrogen atmosphere to obtain the potassium-doped carbon-coated nickel oxide nanocomposite.
FIG. 1 is an X-ray diffraction (XRD) pattern of the product obtained in step (3) of example 1, wherein the nickel in the nanocomposite material is present as an oxide after the mild oxidation treatment, as shown in FIG. 1. FIG. 2 is a Transmission Electron Microscope (TEM) image of the product obtained in step (3) of example 1, and it can be seen from FIG. 2 that the particle size of the nanocomposite is about 5nm to 20 nm. As a result of elemental analysis, the carbon content in the nanocomposite was 0.64wt% and the nickel oxide content was 99.36wt%. As is evident from XPS analysis, the surface layer of the product obtained in the step (3) contains carbon, oxygen and nickel. Wherein the ratio of the surface layer carbon element content to the total carbon element content is 32.7/1, indicating that carbon in the product is mainly present on the surface of the particles. FIG. 3 is a Raman spectrum of the product obtained in the step (3) of example 1, and from FIG. 3, it can be seen that the G peak (1580 cm -1 ) Intensity of (C) and intensity of D peak (1320 cm) -1 ) The ratio of (2) to (1) is 2.2/1, namely the surface of the nano composite material is coated by graphitized carbon film. As is evident from elemental analysis, the carbon content of the product obtained in the step (4) was 0.58wt%, the nickel oxide content was 98.63wt%, and the potassium oxide content was 0.79wt%. As is evident from XPS results, the surface layer of the product obtained in the step (4) contains carbon, oxygen, nickel and potassium. Wherein the potassium content of the surface layer was 1.41mol%.
Example 2
This example is used to illustrate the method of preparing the carbon-coated nickel oxide nanocomposite of the present invention.
(1) 10g of nickel acetate and 10g of citric acid are weighed into a beaker containing 100mL of deionized water, stirred at 70 ℃ to obtain a homogeneous solution, and continuously heated and evaporated to dryness to obtain a solid precursor.
(2) And (3) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow of 100mL/min, heating to 650 ℃ at the speed of 2 ℃/min, stopping heating after keeping the temperature for 2 hours, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel composite material.
(3) And (3) placing the product obtained in the step (2) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing standard gas (the volume concentration of oxygen is 15 percent and nitrogen is balance gas) with the flow rate of 100mL/min, heating to 330 ℃ at the speed of 2 ℃/min, keeping the temperature for 8 hours, stopping heating, and cooling to room temperature under the atmosphere of the standard gas to obtain the graphitized carbon film-coated nickel oxide nanocomposite.
(4) 50ml of deionized water was added to 1.0 g (potassium ca. 0.014 mol) K 2 CO 3 A solution was prepared and 8.5g of the product from step (3) (about 0.14mol of nickel) was added to K 2 CO 3 The solution is evenly mixed and stirred, and after 4 hours; and (3) placing the solid-liquid mixture in an oven at 80 ℃, drying for 12 hours, then placing in a tube furnace, introducing nitrogen, heating to 350 ℃ at a speed of 5 ℃/min, keeping the temperature for 4 hours, stopping heating, and cooling to room temperature under nitrogen atmosphere to obtain the potassium-doped carbon-coated nickel oxide nanocomposite.
FIG. 4 is an X-ray diffraction pattern (XRD) of the product obtained in step (3) of example 2, wherein the nickel in the nanocomposite material is obtained by subjecting the product to a mild oxidation treatment as shown in FIG. 4The oxide form exists. FIG. 5 is a TEM image of the product obtained in step (3) of example 2, and it can be seen from FIG. 5 that the particle size of the nanocomposite is about 5nm to 20 nm. As a result of elemental analysis, the carbon content in the nanocomposite was 0.91wt% and the nickel oxide content was 99.09wt%. As is evident from XPS analysis, the surface layer of the product obtained in the step (3) contains carbon, oxygen and nickel. Wherein the ratio of the carbon element content of the surface layer to the total carbon element content is 22.4/1, and the carbon in the product is mainly present on the surface of the particles. FIG. 6 is a Raman spectrum of the product obtained in the step (3) of example 2, and it can be seen from FIG. 6 that the G peak (1580 cm -1 ) Intensity of (C) and intensity of D peak (1320 cm) -1 ) The ratio of (2) is 2.4/1, namely the surface of the nano composite material is coated by the graphitized carbon film. As is evident from elemental analysis, the carbon content of the product obtained in the step (4) was 0.85wt%, the nickel oxide content was 92.32wt%, and the potassium oxide content was 6.83wt%. As is evident from XPS results, the surface layer of the product obtained in the step (4) contains carbon, oxygen, nickel and potassium. Wherein the potassium content of the surface layer was 9.27mol%.
Comparative example 1
(1) 10g of nickel carbonate and 10g of citric acid are weighed into a beaker containing 100mL of deionized water, stirred at 70 ℃ to obtain a homogeneous solution, and continuously heated and evaporated to dryness to obtain a solid precursor.
(2) And (3) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow of 100mL/min, heating to 600 ℃ at the speed of 4 ℃/min, stopping heating after keeping the temperature for 2 hours, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel composite material.
(3) And (3) placing the product obtained in the step (2) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing standard gas (the volume concentration of oxygen is 15 percent and nitrogen is balance gas) with the flow rate of 100mL/min, heating to 350 ℃ at the speed of 2 ℃/min, keeping the temperature for 8 hours, stopping heating, and cooling to room temperature under the atmosphere of the standard gas to obtain the graphitized carbon film-coated nickel oxide nanocomposite.
Comparative example 2
(1) 10g of nickel acetate and 10g of citric acid are weighed into a beaker containing 100mL of deionized water, stirred at 70 ℃ to obtain a homogeneous solution, and continuously heated and evaporated to dryness to obtain a solid precursor.
(2) And (3) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow of 100mL/min, heating to 650 ℃ at the speed of 2 ℃/min, stopping heating after keeping the temperature for 2 hours, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel composite material.
(3) And (3) placing the product obtained in the step (2) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing standard gas (the volume concentration of oxygen is 15 percent and nitrogen is balance gas) with the flow rate of 100mL/min, heating to 330 ℃ at the speed of 2 ℃/min, keeping the temperature for 8 hours, stopping heating, and cooling to room temperature under the atmosphere of the standard gas to obtain the graphitized carbon film-coated nickel oxide nanocomposite.
Comparative example 3
Placing 10g of nickel acetate solid into a porcelain boat, placing the porcelain boat into a constant temperature area of a tube furnace, introducing air with the flow rate of 150mL/min, heating to 500 ℃ at the speed of 2 ℃/min, stopping heating after keeping the temperature for 2 hours, and cooling to room temperature under the air atmosphere to obtain a sample material.
Fig. 7 is an X-ray diffraction pattern of the material obtained in comparative example 3, and as can be seen from fig. 7, the XRD pattern of the material shows characteristic peaks of nickel oxide, indicating that nickel exists mainly in the form of nickel oxide. Fig. 8a and 8b show transmission electron microscopy images of the material obtained in comparative example 3 at different magnification, respectively, and it can be seen that nickel oxide clusters together in a large amount, which indicates that nickel oxide nanoparticles without carbon film coating are extremely easy to cluster to a large extent. As a result of elemental analysis, the carbon content of the material obtained in comparative example 3 was 0.12% by weight, and the nickel oxide content was 99.88% by weight.
Application example 1
This application example is intended to illustrate the reaction of catalyzing the decomposition of nitrous oxide using the nanocomposite of example 1 as a catalyst.
0.5g of the catalyst was placed in a continuous flow fixed bed reactor, and the reaction gas composition was 38.0% N 2 O, nitrogen was used as an equilibrium gas, and the flow rate of the reaction gas was 15ml/min. The activity evaluation temperature ranges are shown in Table 1, and N is catalytically decomposed 2 The conversion of O is shown in Table 1.
Application example 2
This application example is intended to illustrate the reaction of catalyzing the decomposition of nitrous oxide using the nanocomposite of example 2 as a catalyst.
0.5g of the catalyst was placed in a continuous flow fixed bed reactor, and the reaction gas composition was 38.0% N 2 O, nitrogen was used as an equilibrium gas, and the flow rate of the reaction gas was 15ml/min. The activity evaluation temperature ranges are shown in Table 1, and N is catalytically decomposed 2 The conversion of O is shown in Table 1.
Comparative application example 1
This comparative application example is intended to illustrate the reaction of catalyzing the decomposition of nitrous oxide using the nanocomposite of comparative example 1 as a catalyst.
0.5g of the catalyst was placed in a continuous flow fixed bed reactor, and the reaction gas composition was 38.0% N 2 O, nitrogen was used as an equilibrium gas, and the flow rate of the reaction gas was 15ml/min. The activity evaluation temperature ranges are shown in Table 1, and N is catalytically decomposed 2 The conversion of O is shown in Table 1.
Comparative application example 2
This comparative application example is intended to illustrate the reaction of catalyzing the decomposition of nitrous oxide using the nanocomposite of comparative example 2 as a catalyst.
0.5g of the catalyst was placed in a continuous flow fixed bed reactor, and the reaction gas composition was 38.0% N 2 O, nitrogen was used as an equilibrium gas, and the flow rate of the reaction gas was 15ml/min. The activity evaluation temperature ranges are shown in Table 1, and N is catalytically decomposed 2 The conversion of O is shown in Table 1.
Comparative application example 3
This comparative example is used to illustrate the reaction of catalyzing the decomposition of nitrous oxide using the material of comparative example 3 as a catalyst.
0.5g of the catalyst was placed in a continuous flow fixed bed reactor, and the reaction gas composition was N with a volume concentration of 38.0% 2 O, nitrogen is used as balance gas, the flow rate of reaction gas is 15ml/min, the activity evaluation temperature range is shown in Table 1, and the catalyst is catalyzed at different temperaturesCatalytic decomposition of N 2 The conversion of O is shown in Table 1.
Comparative application example 4
Commercial nickel oxide (NiO) (analytical grade, batch number: 20160803, manufacturer: national drug Co., ltd.) was used as a catalyst, and 0.5 g of commercial nickel oxide was placed in a continuous flow fixed bed reactor, and the reaction gas composition was 38.0% N 2 O, nitrogen was used as an equilibrium gas, and the flow rate of the reaction gas was 15ml/min. The activity evaluation temperature ranges are shown in Table 1, and the catalyst is used for catalytically decomposing N at different temperatures 2 The conversion of O is shown in Table 1.
TABLE 1
As can be seen from Table 1 above, the potassium-doped graphitized carbon film-coated nickel oxide nanocomposite prepared by the method of the present invention has a better N than the non-potassium-doped graphitized carbon film-coated nickel oxide nanocomposite 2 The catalytic decomposition performance of O can efficiently eliminate N at 340-360 DEG C 2 O. The reduction degree of the temperature can greatly reduce the energy consumption and save the production cost in the process of applying the actual industrial production to the treatment of the waste gas in the adipic acid production process, thereby effectively improving the economic benefit and having important practical significance.
It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.
Claims (12)
1. The nanocomposite of carbon-coated nickel oxide is characterized in that the nanocomposite comprises a nuclear membrane structure with an outer membrane and an inner core, the outer membrane is a graphitized carbon membrane, the inner core comprises nickel oxide nanoparticles, the nanocomposite further comprises a second metal, the second metal is an alkali metal and/or an alkaline earth metal, and the molar ratio of the second metal to nickel is 0.01-0.3;
the carbon content is no more than 1wt% of the nanocomposite;
the ratio of carbon element determined by X-ray photoelectron spectroscopy to the content of carbon element determined by elemental analysis in the nanocomposite is not less than 10 in terms of mass ratio;
the Raman spectrum of the nanocomposite is 1580cm -1 G peak intensity in the vicinity and at 1320cm -1 The ratio of nearby D peak intensities is greater than 2;
the particle size of the nuclear membrane structure is 1 nm-100 nm.
2. A method of preparing the carbon-coated nickel oxide nanocomposite of claim 1, comprising the steps of:
Placing a nickel source and a polybasic organic carboxylic acid in a solvent, mixing to form a homogeneous solution, and removing the solvent in the homogeneous solution to obtain a precursor;
the precursor is pyrolyzed in an inert atmosphere or a reducing atmosphere;
oxygen treatment is carried out on the pyrolyzed product;
preparing a second metal salt solution, uniformly mixing the product after oxygen treatment with the second metal salt solution, and stirring to obtain a solid-liquid mixture; a kind of electronic device with high-pressure air-conditioning system
And drying and roasting the solid-liquid mixture to obtain the nanocomposite.
3. The method of claim 2, further comprising acid washing the pyrolyzed product prior to the oxygen treatment.
4. The process according to claim 3, wherein the acid washing loss rate of the product after the acid washing treatment is 40% or less.
5. The preparation method according to claim 2, wherein the mass ratio of the nickel source to the polybasic organic carboxylic acid is 1 (0.1-10); the nickel source is selected from one or more of organic acid salt of nickel, nickel carbonate, basic nickel carbonate, nickel hydroxide and nickel oxide; the polybasic organic carboxylic acid is selected from one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, gluconic acid and malic acid.
6. The method of preparation of claim 2, wherein the pyrolyzing comprises: heating the precursor to a constant temperature section in an inert atmosphere or a reducing atmosphere, and keeping the constant temperature in the constant temperature section; the heating temperature rise rate is 0.5-10 ℃/min, the constant temperature section temperature is 400-800 ℃, the constant temperature time is 20-600 min, the inert atmosphere is nitrogen or argon, and the reducing atmosphere is a mixed gas of inert gas and hydrogen.
7. The method of claim 2, wherein the oxygen treatment comprises introducing a standard gas into the pyrolyzed product and heating, wherein the standard gas contains oxygen and a balance gas, and the volume concentration of the oxygen is 10% -40%.
8. The preparation method according to claim 2, wherein the temperature of the oxygen treatment is 200-500 ℃, and the time of the oxygen treatment is 0.5-10 h.
9. The method of claim 2, wherein the second metal salt solution is selected from one or more of an alkali metal and/or alkaline earth metal organic acid salt solution, a carbonate solution, a basic carbonate solution, a nitrate solution, and a sulfate solution.
10. The preparation method according to claim 2, wherein the drying temperature is 60-100 ℃ and the drying time is 15-25 h; the firing includes: heating the dried product to a constant temperature section, and keeping the constant temperature in the constant temperature section; the heating rate is 0.5-30 ℃/min, the temperature of the constant temperature section is 200-400 ℃, and the constant temperature time is 20-600 min.
11. A method of catalyzing the decomposition of nitrous oxide comprising contacting a catalyst comprising the nanocomposite of claim 1 with nitrous oxide to effect a catalytic decomposition reaction to produce nitrogen and oxygen.
12. The method according to claim 11, wherein in the catalytic decomposition reaction, the reaction temperature is 300 ℃ to 400 ℃, the reaction space velocity is 1000 to 3000 ml of reaction gas/(hour.g of nanocomposite), and the volume concentration of nitrous oxide in the reaction gas is 30% -40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010503592.4A CN113751008B (en) | 2020-06-05 | 2020-06-05 | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010503592.4A CN113751008B (en) | 2020-06-05 | 2020-06-05 | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113751008A CN113751008A (en) | 2021-12-07 |
| CN113751008B true CN113751008B (en) | 2023-07-14 |
Family
ID=78783907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010503592.4A Active CN113751008B (en) | 2020-06-05 | 2020-06-05 | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113751008B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109003825A (en) * | 2018-07-27 | 2018-12-14 | 青岛科技大学 | A kind of nitrogen-doped carbon/nickel nickel nanocomposite preparation method |
| CN109332681A (en) * | 2018-12-06 | 2019-02-15 | 河北工业大学 | Carbon-coated iron-tri-ferrous carbide magnetic nanoparticle preparation method |
| CN110034306A (en) * | 2019-03-13 | 2019-07-19 | 上海交通大学 | The preparation method and application of the composite material of the porous carbon coating cobalt nano-particle of N doping |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7932419B2 (en) * | 2003-08-14 | 2011-04-26 | Monsanto Technology Llc | Transition metal-containing catalysts and processes for their preparation and use as oxidation and dehydrogenation catalysts |
-
2020
- 2020-06-05 CN CN202010503592.4A patent/CN113751008B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109003825A (en) * | 2018-07-27 | 2018-12-14 | 青岛科技大学 | A kind of nitrogen-doped carbon/nickel nickel nanocomposite preparation method |
| CN109332681A (en) * | 2018-12-06 | 2019-02-15 | 河北工业大学 | Carbon-coated iron-tri-ferrous carbide magnetic nanoparticle preparation method |
| CN110034306A (en) * | 2019-03-13 | 2019-07-19 | 上海交通大学 | The preparation method and application of the composite material of the porous carbon coating cobalt nano-particle of N doping |
Non-Patent Citations (1)
| Title |
|---|
| Facile synthesis of N-doped carbon-coated nickel oxide nanoparticle sembedded in N-doped carbon sheets for reversible lithium storage;Zhiqing Jia et al.;Journ al of Alloys and Compounds;第第745卷卷;第147-154页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113751008A (en) | 2021-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109309212B (en) | Carbon-coated cobalt nano composite material and preparation method thereof | |
| CN110201702A (en) | Carbon carries the nitrogenous compound oxygen reduction catalyst preparation method of monoatomic metal and gained catalyst | |
| WO2021078112A1 (en) | Carbon-coated nickel oxide nanocomposite material, preparation method therefor and use thereof | |
| CN112705235A (en) | Carbon-coated nickel carbide nano composite material and preparation method and application thereof | |
| CN113751004B (en) | Catalyst of carbon-coated transition metal oxide, preparation method and application thereof | |
| CN115121110B (en) | Method for catalyzing decomposition of nitrous oxide | |
| CN113751005B (en) | Catalyst of carbon-coated transition metal oxide, preparation method and application thereof | |
| CN113751042B (en) | Carbon-coated nickel oxide nano composite material and preparation method and application thereof | |
| CN113751008B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof | |
| CN113751007B (en) | Catalyst of carbon-coated nickel oxide, preparation method and application thereof | |
| CN113751041B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof | |
| CN113751006B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof | |
| Fu et al. | Oxidative decomposition of chlorobenzene on MnaVOX catalysts: The critical roles of oxygen vacancies and hollow structure | |
| CN113750991B (en) | Catalyst of carbon-coated nickel oxide, preparation method and application thereof | |
| CN112755993B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof | |
| CN112755994A (en) | Carbon-coated nickel-aluminum nano composite material and preparation method and application thereof | |
| CN113750781A (en) | Method for catalytic decomposition of nitrous oxide | |
| CN113751003B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof | |
| CN113757696A (en) | Method for catalytic combustion of volatile organic compounds | |
| EP4049752A1 (en) | Carbon-coated nickel-aluminum nanocomposite, preparation method therefor and application thereof | |
| CN112762469B (en) | Method for catalytic combustion of volatile organic compounds | |
| CN112755780B (en) | Method for catalytic decomposition of nitrous oxide | |
| CN115121252B (en) | Carbon-coated nickel nanocomposite, and preparation method and application thereof | |
| CN113757697A (en) | Method for catalytic combustion of volatile organic compounds | |
| CN112762468A (en) | Method for catalytic combustion of volatile organic compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |