CN106040239A - Controllable high-dispersion nano simple-substance metal/carbon composite material preparation method and electrical catalytic application thereof - Google Patents
Controllable high-dispersion nano simple-substance metal/carbon composite material preparation method and electrical catalytic application thereof Download PDFInfo
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- CN106040239A CN106040239A CN201610358771.7A CN201610358771A CN106040239A CN 106040239 A CN106040239 A CN 106040239A CN 201610358771 A CN201610358771 A CN 201610358771A CN 106040239 A CN106040239 A CN 106040239A
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 31
- 239000000126 substance Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000006185 dispersion Substances 0.000 title claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 title abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 53
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 31
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000009467 reduction Effects 0.000 claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 4
- 230000010412 perfusion Effects 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000003575 carbonaceous material Substances 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 20
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003344 environmental pollutant Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 231100000719 pollutant Toxicity 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229950000845 politef Drugs 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 235000015096 spirit Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005287 template synthesis Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 239000000428 dust Substances 0.000 claims 1
- 239000011799 hole material Substances 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 238000002848 electrochemical method Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000003958 fumigation Methods 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 11
- 229960004756 ethanol Drugs 0.000 description 10
- -1 life Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000001603 reducing effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000001925 catabolic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QSQUFRGBXGXOHF-UHFFFAOYSA-N cobalt(III) nitrate Inorganic materials [Co].O[N+]([O-])=O.O[N+]([O-])=O.O[N+]([O-])=O QSQUFRGBXGXOHF-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 208000005135 methemoglobinemia Diseases 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/50—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Abstract
The invention relates to a controllable high-dispersion nano simple-substance metal/carbon composite material preparation method and electrical catalytic application thereof. An ordered mesoporous carbon powder material having high specific area is synthesized; the material is subjected to oxidation treatment to obtain mesoporous carbon provided with hydrophilic groups on the surface and having high specific area; metal precursor perfusion is performed by adopting an impregnation method, the mesoporous carbon is converted into hydroxide by adopting an ammonia fumigation method, and the hydroxide is fixed in mesoporous confined pore channels; reduction is performed at high temperature in the presence of H2, and finally a high-dispersion nano metal simple-substance/carbon composite material is obtained. With zero-valent iron/mesoporous carbon as an example, the composite material serves as a working electrode, a three-electrode electrochemical method is adopted to remove nitrate in a water body through electrical catalytic reduction. The composite material prepared by adopting the preparation method contains small simple-substance metal nanoparticles which are evenly dispersed in the pore channels of a carbon substrate, and the metal crystallization degree and supporting amount are easy to control in the preparation process. After electrode slices are produced, the nitrate treatment efficiency is high, the nitrogen selectivity is improved, the stability is good, and secondary pollution such as metal ion dissolution is not caused.
Description
Technical field
The invention provides and a kind of use electro-catalysis reduction to remove the nano composite material preparation method of nitrate in water body
And application, belong to pollutant catabolic gene and remove field, relate to a kind of mesoporous carbon-loaded high-load, polymolecularity metal simple-substance nanometer
The preparation method of granular materials.
Background technology
Along with economic fast development, the use of a large amount of chemical nitrogen fertilizers, life, industrial wastewater and the unreasonable place of mud
Putting, in the surface water and groundwater of many countries and regions, nitrate content increases day by day, have become as one fairly common and
Serious environmental problem.In natural water, the rising of nitrogen element can cause body eutrophication and break out wawter bloom, drinking water simultaneously
The absorption of nitrate too much in source, can be converted into nitrite in human body, thus induce methemoglobinemia, sternly
Hypoxia death can be caused during weight.World Health Organization (WHO) specifies NO in drinking water in water quality standard for drinking water3-N concentration is less than
10 mg/L.Therefore, effectively control and process the water source of high azotate pollution and become the task of top priority.
The method of nitrate in water body of removing at present mainly has physics, chemistry and bioanalysis.For comparing, Physical goes
Not there is selectivity except nitrate, the most real degraded of pollutant, simply there occurs transfer or concentrate；The conventional anti-nitre of biology
Nitrate transformation is nitrogen by the reduction of microorganism by change method, but the method capacity of resisting impact load is poor, complex process,
There is secondary pollution problems simultaneously；Chemical reduction method mainly includes metal simple-substance reducing process, catalysis reduction and electrochemical process.Gold
Belong to simple substance reducing process to be mainly with metal simple-substances such as ferrum, aluminum, zinc as reducing agent, have problems in that the product of reaction is difficult to turn
Turn to harmless nitrogen, and the secondary pollution of metal ion etc. can be produced.And be catalyzed reduction using monometallic or bimetallic as
Catalyst reduces nitrate, but typically requires use hydrogen as reducing agent, and hydrogen dissolubility at ambient pressure is little, uses peace
Full property is the best.Electrochemical reducing utilizes electronics for reducing agent, obtains the extensive concern of research worker in recent years.Generally electrochemistry
Often it is used in combination with noble metal catalyst, and electrochemical method is used in combination the application carrying out catalysis reduction with base metal simple substance
Still there is potentiality to be exploited.
Ferrum is a kind of metal cheap and easy to get.Nano zero valence iron, because its particle size is little, reducing activity strong, the most extensively should
The research of all kinds of pollutant removals in water body.In conjunction with nano zero valence iron and the advantage of electrochemical method, use nitre simultaneously
Hydrochlorate carries out being catalyzed reduction can work in coordination with its removal ability of raising.Yet with big specific surface and magnetic, nano zero valence iron is non-
Chang Rongyi reunites, and greatly reduces its effective active position, and during be there is certain nanometer in the environment in material release
Toxicity.Therefore nano zero valence iron is supported on certain carrier, thus can high degree of dispersion nano-particle with prevent reunite, increase
Add its specific surface and active sites, metal can be fixed again and reduce secondary pollution.Ordered mesoporous material is that a class aperture is at 2～50 nm
Material, as novel nano material carrier, have its unique advantage.Especially ordered mesoporous carbon material, has big ratio table
Area and pore volume, pore-size distribution homogeneous and on nanoscale continuously adjustabe, pore passage structure is from one-dimensional adjustable and advise to three-dimensional
Then orderly, morphology controllable, framing structure is stable, advantages of environment protection.Mesoporous carbon is highly stable in water body, its mesopore orbit
Can load, disperse and fix the nano-metal particle of even particle size as the confinement space of nano-particle.It addition, carbon
Material is a kind of good conductive material.Nano zero valence iron granule uniform load, in the duct of mesoporous carbon, can be formed simultaneously
Micropartical electrode.By this compound negative electrode making electrode, collaborative simple substance catalysed reductive energy and chemical property, thus improve right
The clearance of nitrate and selectivity, avoid secondary pollution problem simultaneously.
With mesoporous carbon for the research of support dispersion nano zero valence iron it has been reported that but obtain one by control synthesis and have
Little granule and dispersed and that load capacity is high nano zero valence iron/meso-porous carbon material, be still that a problem with challenge.
For angle prepared by material, nano zero valence iron generally (is had the reagent such as NaBH of strong reducing power by liquid-phase reduction4), carbon heat
Reduction, vapour phase reduction (reducibility gas such as H2), pyrogenic metal predecessor Fe (CO)5Obtain etc. method.For nano zero valence iron
Load, the method using vapour phase reduction is a preferable method of loading.It addition, anti-during vapour phase reduction of ferrum predecessor
Answering process can cause a certain degree of predecessor Species migration and reunion, the introducing that therefore need nonetheless remain for certain technology improves dispersion
Performance.
Summary of the invention
It is an object of the invention to provide the nano metal simple substance/carbon of a kind of polymolecularity, good stability, high reaction activity
Composite, as a example by nano zero valence iron/mesoporous carbon, makes electrode slice by this composite, in conjunction with electrocatalytic denitrification method, reduction
Remove the nitrate in water body.
Nano metal simple substance/the mesoporous carbon composite material of preparation proposed by the invention, is provided stable and can by mesoporous carbon
The carrier of conduction, has big specific surface area；Simultaneously because the confinement effect in mesoporous carbon duct, elemental metals particle size is equal
One, crystallization degree can be controlled by sintering temperature and time, and tenor is adjustable between 1 ~ 70 wt%.
A kind of high-dispersion nano metal simple-substance/carbon composite controllable method for preparing that the present invention proposes, concrete steps are such as
Under:
(1) synthesis has the order mesoporous carbon powder material of high-ratio surface；
(2) oxidant is configured to solution, the order mesoporous carbon powder material mix and blend obtained with step (1), 30～120 DEG C
Under water-bath, stir 0.5～24 hour；Cooling, filtration；It is vacuum dried at 60 DEG C, obtains the meso-porous carbon material of surface oxidation；
(3) meso-porous carbon material of surface oxidation step (2) obtained disperses in ethanol；Metal precursor is dissolved in simultaneously
Ethanol is configured to the solution of 20 wt%；Then both the above solution mixed, stir, make metal precursor be impregnated into mesoporous carbon
In material duct, until ethanol volatilization is dry in fume hood；The meso-porous carbon material being filled with metal precursor obtained is put into
In cuvette, cuvette is placed in the politef bottle equipped with 14 wt% ammonia spirits, keeps solid sample and ammonia
It is not directly contacted with, seals latter 60 DEG C and process 3 hours；Remove sample surfaces solubilized impurity with water and washing with alcohol, filtration, obtain
Load the meso-porous carbon material of this metal hydroxides；
(4) meso-porous carbon material of metal hydroxides step (3) obtained is put in tube furnace, H2/N2Atmosphere at high temperature roasts
Burn, obtain nano metal simple substance/mesoporous carbon composite material.
In the present invention, the order mesoporous carbon powder material described in step (1) is: the FDU series of soft template method synthesis
The one of CMK series (CMK-3, CMK-5) etc. of (FDU-14, FDU-15, FDU-16, FDU-18) or hard template synthesis or several
Kind, or one or several in activated carbon or CNT.
In the present invention, described in step (2), oxidant is the one in nitric acid, hydrogen peroxide, potassium permanganate or Ammonium persulfate.
Or several, the concentration of described oxidant is 0.5～2 M(0.5～the acidifying of 2.0 M sulphuric acid).
In the present invention, metal precursor described in step (3) is the one of ferric nitrate, cobalt nitrate, nickel nitrate；Nano metal
The load capacity of simple substance by changing the addition of metal precursor or can be obtained by secondary or three perfusion control.
In the present invention, after metal precursor is impregnated in the duct of meso-porous carbon material by step (3), ammonia fumigating need to be used
Steaming is translated into the hydroxide of metal and is fixed in described duct.
In the present invention, H used in step (4)2/N2Being the nitrogen atmosphere containing 10% hydrogen under atmosphere, high-temperature roasting temperature is
200～600 DEG C, roasting time is 0.5～4 h, controls H2/N2Gas flow rate is 25～200 mL/min, heating rate is 1 °/
min。
In the present invention, the specific surface area of the nano metal simple substance/carbon composite prepared is 600～1200 cm3/
G, metal nanoparticle is single zero-valent state simple substance, and is dispersed in mesoporous carbon confinement duct, metal nanoparticle particle diameter
It is 3～8 nm.
Nano metal simple substance/the carbon composite that preparation method of the present invention obtains application in electro-catalysis is reduced,
As a example by Zero-valent Iron/carbon composite, nano zero valence iron/carbon composite is made working electrode, use three-electrode electro Chemical
Method, by the nitrate pollutants in electro-catalysis reduction water body.
In the present invention, described working electrode is according to Zero-valent Iron/carbon composite: white carbon black: be dissolved in N-crassitude
The PVDF(10 g/L of ketone) the ratio mix homogeneously of=80 wt%:10 wt%:10 wt%, coat nickel foam (1 cm × 1 cm)
On, baking oven 40～60 DEG C are dried 4～8 hours, and in vacuum drying oven, 120～140 DEG C are dried 8～12 hours, under 20 Mpa pressure
Compacting obtains；The consumption coating the composite on working electrode is 3～5 mg, platinum electrode as to electrode, saturated calomel
Electrode is reference electrode；Voltage-0.4～-4.0 V, reacts 1～24 hour.
In the present invention, containing nitrate initial concentration in described water body is 20～500 mg/L, and electrolyte is sodium chloride, sulfur
One or more in acid sodium, hydrochloric acid or sodium hydroxide, pH value is 2～13.
The present invention has the advantages that and is:
(1) the invention provides the preparation method of a kind of nano metal simple substance/mesoporous carbon composite material.This preparation method is by adopting
With having high-ratio surface, the mesoporous carbon of duct three-dimensional communication is as supporting substrate, by rear perfusion metal precursor ammonification again
The method of hydrogen reducing, obtains high capacity amount, high degree of dispersion, granular size stable homogeneous, the adjustable composite of tenor.
(2) present invention is using nano zero valence iron/carbon composite as the negative electrode of electrochemistry, it is provided that this kind of applicating cooperation profit
By the catalysis reduction of base metal simple substance and the advantage of electrochemical reduction, improve the removal effect of nitrate pollutants in water body
Rate.
(3) above-mentioned composite is during electro-catalysis reduction nitrate, and reactivity is high, the selectivity to nitrogen
Height, good stability, difficult drop-off, decrease the generation of secondary pollution.
Accompanying drawing explanation
Transmission electron microscope (TEM) photo of Fig. 1 nano zero valence iron/mesoporous carbon composite material, is prepared by embodiment 2.
The recycling performance of nitrate is removed in Fig. 2 nano zero valence iron/mesoporous carbon composite material electro-catalysis reduction, uses reality
Execute example 8 material to obtain.
Detailed description of the invention
The present invention is further illustrated below by embodiment.
Embodiment 1
Phenolic resin and the preparation of surface oxidation ordered mesoporous carbon material: first 12.0 g phenol are melted in 40～42 DEG C of water-baths
Melt, add 2.52 g 20%(mass percentage concentration) NaOH aqueous solution, stir 10 minutes, add 20.4 g formalins
(37 wt%), at 70～75 DEG C, back flow reaction 1 hour, is cooled to room temperature.PH value of solution is regulated to neutral with the HCl of 0.6 M.Will
This solution system is placed in 45 DEG C of water-baths decompression distillation 1～2 hour, obtains 14.1 g phenolic resin (molecular weight 200～500).
It is dissolved in 56.2 g dehydrated alcohol, centrifugal segregation NaCl crystal, is configured to the light brown phenolic aldehyde tree that mass fraction is 20%
Fat performed polymer ethanol solution, standby.By 1.6 g nonionic surfactant poly(ethylene oxide)-poly(propylene oxide)-polycyclic oxygen second
Alkane triblock copolymer (Pluronic F127) and 1.0 g 0.2 M HCl join in 8.0 g ethanol, stir l at 40 DEG C
Hour obtain settled solution.It is subsequently adding 2.08 g tetraethyl orthosilicates and the phenolic resin performed polymer second of 5.0 g 20 wt%
Alcoholic solution, and continue to stir 2 hours.Transferring in glass culture dish by the yellow solution of mix homogeneously, ambient temperatare is put and is waved
Send out 8 hours, be dried through 100 DEG C, cooling.The orange-yellow thin-film material obtained is scraped from culture dish, after suitably grinding, at nitrogen
It is heated to 900 DEG C with 2 DEG C/min under gas atmosphere and keeps 2 hours.The black powder obtained is immersed in 10 wt%'s of excess
In HF solution, it is stirred overnight, removes silica component, mesoporous through filtering, wash and obtain after drying the powder of high-ratio surface
Material with carbon element.Then 1.0 M H are configured2SO41 M salpeter solution of acidifying, is mixed and stirred for the meso-porous carbon material obtained, 30
Stirring in water bath 6 hours at DEG C, filter.It is vacuum dried at 60 DEG C, finally gives the powder meso-porous carbon material of surface oxidation.
Embodiment 2
The preparation of the loaded mesoporous material with carbon element of Zero-valent Iron: by the meso-porous carbon material dispersed with stirring of 0.6 g surface oxidation at 8.0 g ethanol
In；Simultaneously by 0.9 g Fe (NO3)3·9H2O dissolves and is configured to the solution that mass fraction is 20 wt% in ethanol, and adds
0.5 mL 0.2 M HCl suppresses Fe (NO3)3·9H2The hydrolysis of O.The solution dissolved is joined the alcoholic dispersion system of carbon,
Continue stirring, until ethanol volatilization is dry in fume hood.Putting in cuvette by the composite obtained, glass tubing is placed in dress
Have in the politef bottle of 14 wt% ammonia spirits, keep sample to be not directly contacted with ammonia, seal rear 60 DEG C of process 3 little
Time, cooling, remove sample surfaces solubilized impurity with water and washing with alcohol, filtration, obtain loading Fe (OH)3Mesoporous carbon material
Material.This composite is put into vacuum drying oven 60 DEG C be dried, place into tube furnace, pure H2/N2(1:10) the lower 400 DEG C of roastings 2 of atmosphere
Hour, finally obtain Zero-valent Iron/mesoporous carbon composite material (resulting materials transmission electron microscope is shown in Fig. 1).
Embodiment 3
The preparation of the loaded mesoporous material with carbon element of cobalt: preparation method such as embodiment 2, except that add 1.0 in material preparation process
g Co(NO3)3·9H2O dissolves and is configured to the solution that mass fraction is 20 wt% in ethanol
Embodiment 4
Electro-catalytic process removes nitrate: first nano zero valence iron/mesoporous carbon composite material is made working electrode.By composite wood
Material, white carbon black and the PVDF(10 g/L being dissolved in N-Methyl pyrrolidone) it is thoroughly mixed into black slurry by the mass ratio of 8:1:1,
Coating (1 cm × 1 cm) in nickel foam, put into 40 DEG C of baking oven and be dried 5 hours, placing in vacuum drying oven 120 DEG C, to be dried 8 little
Time, suppress 2 minutes under 20 Mpa pressure, obtain working electrode sheet.Material about 3 mg/cm of coating on electrode2.Platinum electrode is made
For to electrode, saturated calomel electrode is reference electrode, uses three-electrode method, processes the waste water containing nitrate.Water distribution is 100
Mg/L nitrate nitrogen, 0.02 mol/L sodium chloride.Electrochemistry denitration reaction is carried out under-1.3 V voltages, after reacting 24 hours, inspection
Survey the NO in solution3 -、NO2 -And NH4 +, the clearance of nitrate, N can be calculated2Conversion ratio and unit mass composite
Process capacity (the results are shown in Table 1).
The preparation of embodiment 5 nano zero valence irons/carbon composite and this composite is removed as electrode catalyst reduction
The method of nitrate such as embodiment 1,2,4 in water except that in material preparation process the sintering temperature of hydrogen be 600 DEG C, roasting
1 hour burning time.
Embodiment 6
The preparation of nano zero valence iron/carbon composite and this composite is removed nitrate in water as electrode catalyst reduction
Method such as embodiment 1,2,4 except that during in material preparation process, the load capacity of ferrum is embodiment 2 1/3rd, i.e.
0.3 g Fe(NO3)3·9H2O dissolves and is configured to the solution that mass fraction is 10 wt% in ethanol.
Embodiment 7
The preparation of nano zero valence iron/carbon composite and this composite is removed nitrate in water as electrode catalyst reduction
Method such as embodiment 1,2,4 is except that removing water distribution during nitrate is 50 mg/L nitrate nitrogens.
Embodiment 8
The preparation of nano zero valence iron/carbon composite and this composite is removed nitrate in water as electrode catalyst reduction
Method such as embodiment 1,2,4, except that remove during nitrate, reuses same working electrode sheet, be electrolysed 4 times with
Obtain recycling performance；During removal nitrate, water distribution is 50 mg/L nitrate nitrogen (see figure 2)s.
Table 1 is to be that in embodiment 4-7, the removal of the nano zero valence iron/carbon composite electrochemical reduction nitrate of preparation is imitated
Rate, N2Selectivity and unit mass thereof remove capacity.
Table 1
| Embodiment | Clearance (%) | N2Selectivity (%) | Remove capacity (mg/g) |
| Embodiment 4 | 30.5 | 85 | 435 |
| Embodiment 5 | 33.5 | 82 | 340 |
| Embodiment 6 | 16.8 | 65 | 64 |
| Embodiment 7 | 29.5 | 75 | 235 |
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply the present invention.Ripe
These embodiments obviously easily can be made various amendment by the personnel knowing art technology, and described herein the most former
Ought to use in other embodiments without through performing creative labour.Therefore, the invention is not restricted to embodiment here, ability
Field technique personnel should be the present invention's according to the announcement of the present invention, the improvement made without departing from scope and amendment
Within protection domain.
Claims (10)
1. high-dispersion nano metal simple-substance/carbon composite controllable method for preparing, it is characterised in that specifically comprise the following steps that
(1) synthesis has the order mesoporous carbon powder material of high-ratio surface；
(2) oxidant is configured to solution, the order mesoporous carbon powder material mix and blend obtained with step (1), 30～120 DEG C
Under water-bath, stir 0.5～24 hour；Cooling, filtration；It is vacuum dried at 60 DEG C, obtains the meso-porous carbon material of surface oxidation；
(3) meso-porous carbon material of surface oxidation step (2) obtained disperses in ethanol；
(4) metal precursor dissolving is configured in ethanol the solution of 20 wt%；
(5) solution step (3) and step (4) obtained mixes, stirring, makes metal precursor be impregnated into meso-porous carbon material duct
In, until ethanol volatilization is dry in fume hood, obtain being filled with the meso-porous carbon material of metal precursor；
(6) putting in cuvette by the meso-porous carbon material being filled with metal precursor that step (5) obtains, cuvette is placed in
In politef bottle equipped with 14 wt% ammonia spirits, keep solid sample to be not directly contacted with ammonia, seal at latter 60 DEG C
Manage 3 hours；Remove sample surfaces solubilized impurity with water and washing with alcohol, filtration, obtain loading Jie of this metal hydroxides
Hole material with carbon element；
(7) meso-porous carbon material of metal hydroxides step (6) obtained is put in tube furnace, H2/N2Atmosphere at high temperature roasts
Burn, obtain nano metal simple substance/mesoporous carbon composite material.
Preparation method the most according to claim 1, it is characterised in that: the order mesoporous carbon dust material described in step (1)
Material is: one or several of the FDU series of soft template method synthesis or the CMK series of hard template synthesis, or activated carbon or carbon receives
One or several in mitron.
Preparation method the most according to claim 1, it is characterised in that: described in step (2), oxidant is nitric acid, dioxygen
One or several in water, potassium permanganate or Ammonium persulfate., the concentration of described oxidant is 0.5～2 M.
Preparation method the most according to claim 1, it is characterised in that: metal precursor described in step (3) be ferric nitrate,
Cobalt nitrate, the one of nickel nitrate；The load capacity of nano metal simple substance is by changing the addition of metal precursor or by two
Secondary or three perfusion control obtains.
Preparation method the most according to claim 1, it is characterised in that: metal precursor is impregnated into by step (3) mesoporous
After in the duct of material with carbon element, ammonia need to be used to fumigate and to be translated into the hydroxide of metal and be fixed in described duct.
Preparation method the most according to claim 1, it is characterised in that: H used in step (4)2/N2It is containing 10% hydrogen under atmosphere
The nitrogen atmosphere of gas, high-temperature roasting temperature is 200～600 DEG C, and roasting time is 0.5～4 h, controls H2/N2Gas flow rate is 25
～200 mL/min, heating rate is 1 °/min.
Preparation method the most according to claim 1, it is characterised in that: the nano metal simple substance/carbon composite wood prepared
The specific surface area of material is 600～1200 cm3/ g, metal nanoparticle is single zero-valent state simple substance, and is dispersed in mesoporous carbon
In confinement duct, metal nanoparticle particle diameter is 3～8 nm.
8. nano metal simple substance/carbon composite that arbitrary preparation method obtains in a kind such as claim 1-7 is in electro-catalysis also
Application in former, it is characterised in that: nano zero valence iron/carbon composite is made working electrode, uses three-electrode electro Chemical side
Method, by the nitrate pollutants in electro-catalysis reduction water body.
Application the most according to claim 8, it is characterised in that: described working electrode is according to Zero-valent Iron/carbon composite:
White carbon black: be dissolved in the PVDF(10 g/L of N-Methyl pyrrolidone) the ratio mix homogeneously of=80 wt%:10 wt%:10 wt%, it is coated with
Being distributed in nickel foam (1 cm × 1 cm), baking oven 40～60 DEG C are dried 4～8 hours, in vacuum drying oven 120～140 DEG C be dried 8～
12 hours, suppress under 20 Mpa pressure and obtain；The consumption coating the composite on working electrode is 3～5 mg, platinum electricity
Pole is as to electrode, and saturated calomel electrode is reference electrode；Voltage-0.4～-4.0 V, reacts 1～24 hour.
Application the most according to claim 8, it is characterised in that: in described water body containing nitrate initial concentration be 20～
500 mg/L, electrolyte is one or more in sodium chloride, sodium sulfate, hydrochloric acid or sodium hydroxide, and pH value is 2～13.
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