CN114618469A - Supported zinc oxide catalyst and preparation method and application thereof - Google Patents
Supported zinc oxide catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN114618469A CN114618469A CN202011475672.XA CN202011475672A CN114618469A CN 114618469 A CN114618469 A CN 114618469A CN 202011475672 A CN202011475672 A CN 202011475672A CN 114618469 A CN114618469 A CN 114618469A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- zinc
- solution
- zinc oxide
- noble metal
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 76
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 29
- 229910000510 noble metal Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 239000004246 zinc acetate Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- AEEAZFQPYUMBPY-UHFFFAOYSA-N [I].[W] Chemical compound [I].[W] AEEAZFQPYUMBPY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 239000002057 nanoflower Substances 0.000 claims description 2
- 239000002073 nanorod Substances 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 239000000956 alloy Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 55
- 238000011156 evaluation Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 10
- 238000001027 hydrothermal synthesis Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 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 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 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
- B01J23/76—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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a catalyst for preparing methanol by photocatalytic methane conversion and a preparation method thereof, which can be used for solving the problems of low catalytic activity and low product selectivity of methane conversion under mild conditions. The catalyst adopted by the invention comprises the following components in percentage by mass: a) the zinc oxide accounts for 90 to 99.9 percent; b) is selected from one or more than two of metals Fe, Co, Ni, Cu, Mn and La, and accounts for 0.1-10% of the total weight of the alloy. The catalyst provided by the invention can realize the high-efficiency activation and directional conversion of the photocatalytic methane to prepare the methanol under mild conditions, and has the characteristics of low price, easy obtainment, high selectivity of methanol products, good recycling performance, no need of strong oxidant in the reaction process and the like.
Description
Technical Field
The invention relates to the technical field of energy chemistry, in particular to a supported zinc oxide catalyst, a preparation method thereof and application thereof in preparing methanol by photocatalytic methane conversion.
Background
Methane is an important energy molecule and widely exists in mineral resources such as natural gas, shale gas, combustible ice and the like (adv. sci.,2020,2001946). Therefore, the high-efficiency catalytic conversion of methane to methanol, formic acid, ethanol, acetic acid, olefin, aromatic hydrocarbon and other high-value-added chemicals is of great importance. However, the tetrahedral structure of the methane molecule itself causes the methane molecule to have the characteristics of strong symmetry, high carbon-hydrogen bond energy (Δ HC-H ═ 104kcal/mol) and the like (chem.rev.,2017,117, 8497-. While solar energy is a rich clean renewable energy source, it is reported that photocatalytic methane conversion can be realized under mild conditions, and thus has attracted extensive attention of researchers (Joule,2019,3, 1606-1636).
At present, various catalysts are used in the process of preparing methanol by methane photocatalytic conversion, for example: WO3(Catal.Commun.,2015,58,200-203;Appl.Catal.B:Environ.,2015,163,150-155)、BiVO4(ACS Catal.,2014,4,3013-2(nat. Catal.,2018,1,889-896), and the like. However, these catalysts usually need to be carried out with the aid of oxidizing agents (oxygen, hydrogen peroxide or nitric oxide) or under deep ultraviolet light conditions, and the methanol yield and selectivity are not ideal. In addition, Au/ZnO is reported to be used for preparing C1 oxygen-containing compound (J.Am.chem.Soc.,2019,141,20507-20515) by converting methane and oxygen under the condition of room temperature by sunlight catalysis, but Au is expensive as a noble metal.
Therefore, the development of cheap and easily-obtained catalyst for preparing methanol by photocatalytic high-efficiency conversion of methane without the participation of strong oxidant has very important significance.
Disclosure of Invention
Based on the technical problems, the invention provides a supported zinc oxide catalyst for preparing methanol by photocatalytic methane conversion, and the high-added-value oxygen-containing compound can be prepared by efficiently and directionally catalyzing and converting methane under mild conditions.
The technical means adopted by the invention are as follows:
a non-noble metal supported zinc oxide catalyst comprises 90-99.9% of zinc oxide carrier and 0.1-10% of non-noble metal by mass percent; the non-noble metal is one or more of Fe, Co, Ni, Cu, Mn and La.
Furthermore, the zinc oxide carrier is in any shape of a nanowire, a nanosheet, a nanorod or a nanoflower, and the mass percentage of the zinc oxide carrier is 95-99.5%; the non-noble metal is any one or more than two of Cu, Fe, Co, Mn or Ni, and the mass percentage content is 0.5-5%.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
(1) preparing a zinc oxide carrier: (a) mixing a zinc source, a precipitator and a surfactant, dissolving the mixture in water, stirring for 0.5-2 hours until the mixture is completely dissolved, transferring the mixture into a hydrothermal kettle, and keeping the mixture in a hydrothermal oven at 80-150 ℃ for 6-48 hours;
(b) centrifuging the product obtained in the step (a) to remove unreacted raw materials, washing with deionized water, and drying at 60-120 ℃ for 6-24 hours;
(c) roasting the product obtained in the step (b) for 1-6 h at the temperature of 300-700 ℃;
(2) dissolving non-noble metal soluble salt in deionized water to prepare a solution A, wherein the concentration of non-noble metal ions is 0.001-10 mol/L;
(3) dropwise adding the solution A into a zinc oxide carrier, or pouring the zinc oxide carrier into the solution A, uniformly mixing, and soaking and stirring at room temperature for 1-48 h;
the mass ratio of the solution A to the zinc oxide carrier is 0.001-100;
(4) drying the mixture obtained in the step (3) at the temperature of 60-120 ℃ for 4-24 hours;
(5) roasting the mixture obtained in the step (4) at 300-700 ℃ for 0.5-2 h.
Further, the zinc source is one or more than two of zinc nitrate, zinc acetate, zinc acetylacetonate, zinc chloride or zinc sulfate; the precipitant is one or more of urea, hexamethylenetetramine, sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate or potassium carbonate; the surfactant is one or more of polyvinylpyrrolidone (PVP), F-127, Cetyl Trimethyl Ammonium Bromide (CTAB) or Sodium Dodecyl Sulfate (SDS); the mass ratio of the zinc source to the precipitating agent to the surfactant is 1:0.1: 0.01-1: 10: 0.5.
Furthermore, the roasting temperature rise rate in the preparation of the zinc oxide carrier is 0.5-10 ℃/min.
Further, the non-noble metal soluble salt is one or two or more of nitrate, sulfate, chloride, acetate or acetylacetone salt of corresponding non-noble metal.
Further, in the step (5), the temperature rise rate of the roasting is 2-10 ℃/min; the roasting atmosphere is one or two of air, argon, nitrogen or hydrogen.
The invention also provides an application of the catalyst in a reaction of preparing methanol by photocatalytic methane conversion.
Further, the light source in the photocatalysis is any one of a xenon lamp, a high-pressure mercury lamp, an LED lamp or a iodine tungsten lamp.
Further, the reaction is that methane and water are stirred in a reaction kettle under the condition of the catalyst to generate methanol; the mass ratio of the catalyst to the water is 1: 10-10: 1; the volume of the reaction kettle is 10-200 mL; the stirring speed is 100-1000 r/min; the reaction pressure is 1-60 bar, the reaction temperature is 25-150 ℃, and the reaction time is 0.1-24 h.
Compared with the prior art, the invention has the following advantages:
1. the catalyst provided by the invention is used for photocatalytic methane conversion reaction, and the obtained product methanol has high yield and selectivity and excellent recycling performance.
2. The catalyst is beneficial to the realization of high-efficiency conversion of methane to prepare high-value-added chemicals such as methanol under mild conditions, does not need the participation of a strong oxidant, has mild reaction process conditions, is environment-friendly, and embodies good economic value.
3. The catalyst provided by the invention does not use noble metal, has low price and simple preparation method, can modulate a zinc source, a precipitator, a surfactant and a load metal, and is easy for batch production.
Detailed Description
The catalysts and their use according to the invention are further illustrated by the following examples, without however limiting the scope of the claims to these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be satisfied to achieve the object.
Example 1
2.0g of zinc acetate is weighed and dissolved in deionized water, 2.0g of urea and 0.2g of PVP are respectively added into the solution, and the solution is stirred for 30min until the dissolution is complete. The resulting mixed solution was transferred to a hydrothermal reaction kettle and maintained at 95 ℃ for 24 hours. After cooling to room temperature, centrifuging, washing and drying at 80 ℃ for 12 h. And roasting the obtained sample for 4 hours at 500 ℃ in a muffle furnace to obtain a ZnO-1 sample.
10mL of a prepared 0.005mol/L copper nitrate solution was taken, 200mg of a ZnO-1 sample was dispersed in the solution, and the solution was immersed under stirring at room temperature and then dried at 80 ℃ for 12 hours. The obtained sample is ground and then roasted for 1h at 500 ℃ to obtain the catalyst Cat 1.
The evaluation reaction condition of the catalyst is that the methane pressure is 24bar, the ratio of the catalyst to water is 1mg/mL, the reaction temperature is 50 ℃, the reaction time is 2h, and the stirring speed is 500 r/min.
Example 2
2.0g of zinc acetate is weighed and dissolved in deionized water, 2.0g of urea and 0.2g of PVP are respectively added into the solution, and the solution is stirred for 30min until the dissolution is complete. The resulting mixed solution was transferred to a hydrothermal reaction kettle and maintained at 95 ℃ for 24 hours. After cooling to room temperature, centrifuging, washing and drying at 80 ℃ for 12 h. And roasting the obtained sample for 4 hours at 300 ℃ in a muffle furnace to obtain a ZnO-2 sample.
10mL of a prepared 0.01mol/L lanthanum acetate solution was taken, 200mg of ZnO-2 sample was dispersed in the solution, immersed with stirring at room temperature, and dried at 80 ℃ for 12 hours. The obtained sample is ground and then roasted for 1h at 500 ℃ to obtain the catalyst Cat 2.
The evaluation reaction condition of the catalyst is that the methane pressure is 1bar, the ratio of the catalyst to water is 1mg/mL, the reaction temperature is 50 ℃, the reaction time is 2h, and the stirring speed is 500 r/min.
Example 3
2.0g of zinc acetate is weighed and dissolved in deionized water, 1.0g of urea and 0.2g of PVP are respectively added into the solution, and the solution is stirred for 30min until the dissolution is complete. The resulting mixed solution was transferred to a hydrothermal reaction kettle and maintained at 95 ℃ for 24 hours. After cooling to room temperature, centrifuging, washing and drying at 80 ℃ for 12 h. And roasting the obtained sample for 4 hours at 500 ℃ in a muffle furnace to obtain a ZnO-3 sample.
10mL of a prepared 0.001mol/L copper nitrate solution was dispersed in a weighed 200mg of ZnO-3 sample, immersed under stirring at room temperature, and dried at 80 ℃ for 12 hours. The sample was ground and then incubated at 300 ℃ H2Roasting for 1h in an Ar atmosphere to obtain the catalyst Cat 3.
The evaluation reaction condition of the catalyst is that the methane pressure is 24bar, the ratio of the catalyst to water is 1mg/mL, the reaction temperature is 50 ℃, the reaction time is 2h, and the stirring speed is 500 r/min.
Example 4
2.0g of zinc acetate is weighed and dissolved in deionized water, 2.0g of urea and 1g of PVP are respectively added into the solution, and the solution is stirred for 30min until the solution is completely dissolved. The resulting mixed solution was transferred to a hydrothermal reaction kettle and maintained at 95 ℃ for 24 hours. After cooling to room temperature, centrifuging, washing and drying at 80 ℃ for 12 h. And roasting the obtained sample for 1h at 500 ℃ in a muffle furnace to obtain a ZnO-4 sample.
10mL of a prepared 2mol/L copper nitrate solution was taken, 200mg of ZnO-4 sample was dispersed in the solution, and the solution was immersed under stirring at room temperature and then dried at 80 ℃ for 12 hours. And grinding the obtained sample, and roasting at 700 ℃ for 1h to obtain the catalyst Cat 4.
The evaluation reaction condition of the catalyst is that the methane pressure is 10bar, the ratio of the catalyst to water is 1mg/mL, the reaction temperature is 50 ℃, the reaction time is 12h, and the stirring speed is 500 r/min.
Example 5
2.0g of zinc acetate is weighed and dissolved in deionized water, 2.0g of urea and 0.2g F-127 are respectively added into the solution, and the mixture is stirred for 30min until the dissolution is complete. The resulting mixed solution was transferred to a hydrothermal reaction kettle and maintained at 95 ℃ for 24 hours. After cooling to room temperature, centrifuging, washing and drying at 80 ℃ for 12 h. And roasting the obtained sample for 4 hours at 500 ℃ in a muffle furnace to obtain a ZnO-5 sample.
10mL of a prepared 0.05mol/L copper nitrate solution was taken, 200mg of ZnO-5 sample was dispersed in the solution, and the solution was immersed under stirring at room temperature and then dried at 120 ℃ for 12 hours. The obtained sample is ground and then roasted for 2h at 500 ℃ to obtain the catalyst Cat 5.
The evaluation reaction condition of the catalyst is that the methane pressure is 40bar, the ratio of the catalyst to water is 0.5mg/mL, the reaction temperature is 50 ℃, the reaction time is 1h, and the stirring speed is 500 r/min.
Example 6
2.0g of zinc acetate is weighed and dissolved in deionized water, 2.0g of urea and 0.2g of PVP are respectively added into the solution, and the solution is stirred for 30min until the dissolution is complete. The resulting mixed solution was transferred to a hydrothermal reaction kettle and maintained at 95 ℃ for 24 hours. After cooling to room temperature, centrifuging, washing and drying at 80 ℃ for 12 h. And roasting the obtained sample for 4 hours at 500 ℃ in a muffle furnace to obtain a ZnO-6 sample.
10mL of a prepared 0.01mol/L ferric nitrate solution was taken, 200mg of a ZnO-6 sample was dispersed in the solution, and after dipping with stirring at room temperature, the solution was dried at 80 ℃ for 12 hours. The obtained sample is ground and then roasted for 1h at 500 ℃ to obtain the catalyst Cat 6.
The evaluation reaction condition of the catalyst is that the methane pressure is 24bar, the ratio of the catalyst to water is 1mg/mL, the reaction temperature is 50 ℃, the reaction time is 2h, and the stirring speed is 500 r/min.
Example 7
2.0g of zinc nitrate is weighed and dissolved in deionized water, 2.0g of hexamethylenetetramine and 0.2g of PVP are respectively added into the solution, and the solution is stirred for 30min until the zinc nitrate is completely dissolved. The resulting mixed solution was transferred to a hydrothermal reaction kettle and maintained at 110 ℃ for 24 hours. After cooling to room temperature, centrifuging, washing and drying at 80 ℃ for 12 h. And roasting the obtained sample for 4 hours at 500 ℃ in a muffle furnace to obtain a ZnO-7 sample.
10mL of a prepared 0.05mol/L copper chloride solution was taken, 500mg of a ZnO-7 sample was dispersed in the solution, and after stirring and immersion at room temperature, the solution was dried at 80 ℃ for 12 hours. The obtained sample is ground and then roasted for 1h at 500 ℃ to obtain the catalyst Cat 7.
The evaluation reaction condition of the catalyst is that the methane pressure is 24bar, the ratio of the catalyst to water is 1mg/mL, the reaction temperature is 25 ℃, the reaction time is 24h, and the stirring speed is 500 r/min.
Example 8
2.0g of zinc acetate is weighed and dissolved in deionized water, 2.0g of urea and 0.2g of PVP are respectively added into the solution, and the mixture is stirred for 30min until the solution is completely dissolved. The resulting mixed solution was transferred to a hydrothermal reaction kettle and maintained at 95 ℃ for 24 hours. After cooling to room temperature, centrifugation, washing and drying at 80 ℃ for 6 h. And roasting the obtained sample for 4 hours at 500 ℃ in a muffle furnace to obtain a ZnO-8 sample.
10mL of a prepared 0.01mol/L copper nitrate solution was taken, and 200mg of a ZnO-8 sample was dispersed in the solution, immersed under stirring at room temperature, and then dried at 60 ℃ for 12 hours. The obtained sample is ground and then roasted for 2h at 500 ℃ to obtain the catalyst Cat 8.
The evaluation reaction condition of the catalyst is that the methane pressure is 24bar, the ratio of the catalyst to water is 10mg/mL, the reaction temperature is 50 ℃, the reaction time is 2h, and the stirring speed is 100 r/min.
Example 9
And taking the catalyst Cat1 after the reaction, washing, drying in vacuum at 80 ℃ for 12h, reacting again, and recording the catalyst after 10 times of circulation as Cat 1-af.
The catalytic evaluation reaction condition is that the methane pressure is 24bar, the ratio of the catalyst to water is 10mg/mL, the reaction temperature is 50 ℃, the reaction time is 2h, and the stirring speed is 500 r/min.
Comparative example 1
1.98g of zinc acetate and 0.02g of copper acetate are weighed and dissolved in deionized water, 2.0g of urea and 0.2g of PVP are respectively added into the solution, and the solution is stirred for 30min until the dissolution is complete. The resulting mixed solution was transferred to a hydrothermal reaction kettle and maintained at 95 ℃ for 24 hours. After cooling to room temperature, centrifuging, washing and drying at 80 ℃ for 12 h. And roasting the obtained sample for 4 hours at 500 ℃ in a muffle furnace to obtain a doped Cu-ZnO sample.
The evaluation reaction condition of the catalyst is that the methane pressure is 24bar, the ratio of the catalyst to water is 1mg/mL, the reaction temperature is 50 ℃, the reaction time is 2h, and the stirring speed is 500 r/min.
Comparative example 2
2.0g of zinc acetate is weighed and dissolved in deionized water, 2.0g of urea and 0.2g of PVP are respectively added into the solution, and the solution is stirred for 30min until the dissolution is complete. The resulting mixed solution was transferred to a hydrothermal reaction kettle and maintained at 95 ℃ for 24 hours. After cooling to room temperature, centrifugation, washing and drying at 80 ℃ for 6 h. And roasting the obtained sample for 4 hours at 500 ℃ in a muffle furnace to obtain a ZnO-1 sample.
10mL of a prepared 0.001mol/L chloroauric acid solution were taken, the pH was adjusted to 9.0 with NaOH, 200mg of a ZnO-1 sample was weighed into the above solution, stirred at room temperature and kept at pH 9.0 for 1h, and then the solution was left to stand at 60 ℃ for 1 h. Suction filtration, washing and drying at 60 ℃ for 12 h. The Au/ZnO catalyst is obtained.
The evaluation reaction condition of the catalyst is that the methane pressure is 24bar, the ratio of the catalyst to water is 1mg/mL, the reaction temperature is 50 ℃, the reaction time is 2h, and the stirring speed is 500 r/min.
Comparative example 3
0.2mL of a prepared 0.005mol/L copper nitrate solution was weighed out, and 200mg of P25 sample was dispersed in the solution. After stirring and dipping at room temperature, the mixture was dried at 80 ℃ for 12 hours. The obtained sample is ground and then roasted for 1h at 500 ℃ to obtain the Cu/P25 catalyst.
The evaluation reaction condition of the catalyst is that the methane pressure is 24bar, the ratio of the catalyst to water is 1mg/mL, the reaction temperature is 50 ℃, the reaction time is 2h, and the stirring speed is 500 r/min.
Comparative example 4
0.2mL of a prepared 0.005mol/L copper nitrate solution was weighed out to obtain 200mg of WO3The sample is dispersed into the above solution. After stirring and impregnation at room temperature, the mixture was dried at 80 ℃ for 12 hours. Grinding the obtained sample, and roasting at 500 ℃ for 1h to obtain Cu/WO3A catalyst.
The evaluation reaction condition of the catalyst is that the methane pressure is 24bar, the ratio of the catalyst to water is 1mg/mL, the reaction temperature is 50 ℃, the reaction time is 2h, and the stirring speed is 500 r/min.
Test example
The evaluation results of the photocatalytic methane conversion to methanol reaction performance of the catalysts of the above examples and comparative examples under different reaction conditions are shown in table 1.
TABLE 1 evaluation results of reaction Properties
According to the results, the prepared M/ZnO catalyst can better realize the photocatalytic conversion of methane to methanol, and the yield of the methanol can reach 180 mu mol g-1h-1Above, the selectivity of the methanol is more than 60 percent, and can reach more than 90 percent under the optimal condition. Under the same test conditions, the performance of the catalyst is far better than that of a doped zinc oxide catalyst, a noble metal catalyst and other carrier (such as titanium oxide and tungsten oxide) catalysts. And the catalyst shows better recycling performance, and the yield and the selectivity of the methane do not change obviously after 10 times of circulation.
The catalyst prepared by the invention is never used in a reaction system for preparing methanol by photocatalysis of methane under a mild condition, shows excellent methanol yield and selectivity, and is expected to realize more economic values.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A non-noble metal supported zinc oxide catalyst is characterized by comprising 90-99.9% of zinc oxide carrier and 0.1-10% of non-noble metal by mass percent; the non-noble metal is any one or more than two of Fe, Co, Ni, Cu, Mn or La.
2. The catalyst of claim 1, wherein the zinc oxide carrier has a morphology of any one of nanowires, nanosheets, nanorods or nanoflowers, and is 95-99.5% by mass; the non-noble metal is any one or more than two of Cu, Fe, Co, Mn or Ni, and the mass percentage content is 0.5-5%.
3. A method for preparing a catalyst according to claim 1 or 2, comprising the steps of:
(1) preparing a zinc oxide carrier: (a) mixing a zinc source, a precipitator and a surfactant, dissolving the mixture in water, stirring for 0.5-2 hours until the mixture is completely dissolved, and keeping the mixture at 80-150 ℃ for 6-48 hours;
(b) centrifuging the product obtained in the step (a) to remove unreacted raw materials, washing with deionized water, and drying at 60-120 ℃ for 6-24 hours;
(c) roasting the product obtained in the step (b) for 1-6 h at the temperature of 300-700 ℃;
(2) dissolving non-noble metal soluble salt in deionized water to prepare a solution A, wherein the concentration of non-noble metal ions is 0.001-10 mol/L;
(3) dropwise adding the solution A into a zinc oxide carrier, or pouring the zinc oxide carrier into the solution A, uniformly mixing, and soaking and stirring at room temperature for 1-48 h;
the mass ratio of the solution A to the zinc oxide carrier is 0.001-100;
(4) drying the mixture obtained in the step (3) at the temperature of 60-120 ℃ for 4-24 hours;
(5) roasting the mixture obtained in the step (4) at 300-700 ℃ for 0.5-2 h.
4. The method according to claim 3, wherein the zinc source is one or more of zinc nitrate, zinc acetate, zinc acetylacetonate, zinc chloride, and zinc sulfate; the precipitator is one or more than two of urea, hexamethylenetetramine, sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate or potassium carbonate; the surfactant is one or more than two of polyvinylpyrrolidone (PVP), F-127, Cetyl Trimethyl Ammonium Bromide (CTAB) or Sodium Dodecyl Sulfate (SDS); the mass ratio of the zinc source to the precipitator to the surfactant is 1:0.1: 0.01-1: 10: 0.5.
5. The preparation method according to claim 3, wherein the roasting temperature rise rate in the preparation of the zinc oxide carrier is 0.5-10 ℃/min.
6. The method according to claim 3, wherein the non-noble metal soluble salt is one or more of nitrate, sulfate, chloride, acetate or acetylacetonate of a corresponding non-noble metal.
7. The production method according to claim 3, wherein in the step (5), the temperature increase rate of the calcination is 2 ℃/min to 10 ℃/min; the roasting atmosphere is one or two of air, argon, nitrogen or hydrogen.
8. Use of the catalyst according to claim 1 or 2 for photocatalytic methane conversion to methanol.
9. The use according to claim 8, wherein the light source in the photocatalysis is any one of xenon lamp, high pressure mercury lamp, LED lamp or iodine tungsten lamp.
10. The use of claim 8, wherein the reaction is the agitation of methane and water in a reaction kettle under the condition of the catalyst to produce methanol; the mass ratio of the catalyst to the water is 1: 10-10: 1; the volume of the reaction kettle is 10-200 mL; the stirring speed is 100-1000 r/min; the reaction pressure is 1-60 bar, the reaction temperature is 25-150 ℃, and the reaction time is 0.1-24 h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011475672.XA CN114618469A (en) | 2020-12-14 | 2020-12-14 | Supported zinc oxide catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011475672.XA CN114618469A (en) | 2020-12-14 | 2020-12-14 | Supported zinc oxide catalyst and preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114618469A true CN114618469A (en) | 2022-06-14 |
Family
ID=81896802
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011475672.XA Pending CN114618469A (en) | 2020-12-14 | 2020-12-14 | Supported zinc oxide catalyst and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114618469A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115069285A (en) * | 2022-06-14 | 2022-09-20 | 太原理工大学 | Photo-thermal catalyst for directly preparing methanol from methane, and preparation method and application thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5720858A (en) * | 1996-07-17 | 1998-02-24 | The United States Of America As Represented By The United States Department Of Energy | Method for the photocatalytic conversion of methane |
CN104671276A (en) * | 2013-11-28 | 2015-06-03 | 上海工程技术大学 | Synthetic method for three-dimensional structure assembled by La surface-modified ZnO nanosheets |
CN106268800A (en) * | 2016-07-15 | 2017-01-04 | 宁波工程学院 | The application in high efficiency photocatalyst of the Ag loading ZnO full meso-porous nano fiber |
CN107233889A (en) * | 2017-05-03 | 2017-10-10 | 昆明理工大学 | A kind of preparation method of Cu/ZnO photochemical catalysts |
CN111167512A (en) * | 2020-03-04 | 2020-05-19 | 南京工程学院 | Novel photo-thermal catalyst for synthesizing methanol by oxidizing methane and preparation method thereof |
CN111333487A (en) * | 2020-04-16 | 2020-06-26 | 广州大学 | Method for preparing methanol by photocatalytic oxidation of methane |
-
2020
- 2020-12-14 CN CN202011475672.XA patent/CN114618469A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5720858A (en) * | 1996-07-17 | 1998-02-24 | The United States Of America As Represented By The United States Department Of Energy | Method for the photocatalytic conversion of methane |
CN104671276A (en) * | 2013-11-28 | 2015-06-03 | 上海工程技术大学 | Synthetic method for three-dimensional structure assembled by La surface-modified ZnO nanosheets |
CN106268800A (en) * | 2016-07-15 | 2017-01-04 | 宁波工程学院 | The application in high efficiency photocatalyst of the Ag loading ZnO full meso-porous nano fiber |
CN107233889A (en) * | 2017-05-03 | 2017-10-10 | 昆明理工大学 | A kind of preparation method of Cu/ZnO photochemical catalysts |
CN111167512A (en) * | 2020-03-04 | 2020-05-19 | 南京工程学院 | Novel photo-thermal catalyst for synthesizing methanol by oxidizing methane and preparation method thereof |
CN111333487A (en) * | 2020-04-16 | 2020-06-26 | 广州大学 | Method for preparing methanol by photocatalytic oxidation of methane |
Non-Patent Citations (3)
Title |
---|
XUXING CHEN ET AL.: "Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts", 《NATURE COMMUNICATIONS》 * |
ZHONGHUA LI ET AL.: "Photocatalytic oxidation of methane over CuO-decorated ZnO nanocatalysts", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
董丽红: "《两亲分子在纳米技术领域中的应用》", 31 October 2013, 吉林大学出版社 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115069285A (en) * | 2022-06-14 | 2022-09-20 | 太原理工大学 | Photo-thermal catalyst for directly preparing methanol from methane, and preparation method and application thereof |
CN115069285B (en) * | 2022-06-14 | 2024-01-16 | 太原理工大学 | Photo-thermal catalyst for directly preparing methanol from methane and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103071492A (en) | Preparation method of efficient formaldehyde catalytic conversion catalyst | |
CN112755996A (en) | Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application | |
CN112371173B (en) | Platinum-carbon catalyst applied to hydrogenation of m-nitrobenzenesulfonic acid and preparation method thereof | |
CN102101051B (en) | Method for preparing carbon nano tube supported nano photocatalysis material capable of degrading nitrogen oxides | |
CN109364931A (en) | A kind of hydrogenation of carbon dioxide catalyst for methanol of core-shell structure and preparation method thereof | |
CN109647501A (en) | A kind of multi-stage porous Fe- beta-molecular sieve catalyst and its preparation method and application | |
CN110711577B (en) | PtRu partially embedded three-dimensional ordered macroporous Ce 0.7 Zr 0.3 O 2 High stability catalyst of | |
CN114618469A (en) | Supported zinc oxide catalyst and preparation method and application thereof | |
CN110252317B (en) | Ce-Fe-based catalyst for efficiently removing nitrogen oxides at low temperature | |
CN105498780B (en) | A kind of Cu/ZnO catalyst and preparation method thereof and in CO2Application in chemical conversion | |
CN114733520A (en) | Preparation method and application of supported nano-gold catalyst | |
CN114377709A (en) | Hydrothermal method for preparing CeO2/Ce(OH)CO3Method of heterojunction | |
CN115722223A (en) | Nano copper-based catalyst, preparation and application thereof in hydrogenation reaction | |
WO2022126843A1 (en) | Ternary composite material having nio nanosheet/bimetallic cecuox microsheet core-shell structure, and preparation and application thereof | |
CN110048131A (en) | A kind of preparation method of high efficiency methanol oxidation catalyst | |
CN114558566B (en) | Hydrogen sulfide selective oxidation catalyst and preparation method and application thereof | |
CN111589464B (en) | Boron nitride-loaded rhodium-gallium-tin liquid alloy catalyst and preparation method and application thereof | |
CN117563645A (en) | Composite photocatalyst based on surface aminated carbon nitride, preparation method and application | |
CN114308061B (en) | NiAu bimetallic alloy nano-catalyst and synthesis and application thereof | |
CN115055200B (en) | Cu (copper) alloy 2 Preparation method of O/HBN composite material and nitrogen fixation application | |
CN117427643B (en) | Photocatalytic material based on graphite-phase carbon nitride and preparation method and application thereof | |
CN116422342B (en) | Multi-atom doped surface platinum-rich catalyst and preparation method thereof | |
CN112844396B (en) | Copper/cerium lanthanum composite oxide nanorod catalyst, preparation method and application | |
CN109046398B (en) | Mn-based non-noble metal catalyst for CO dehydrogenation and purification and preparation method thereof | |
CN117920207A (en) | Gallium-containing alloy system catalyst applied to propylene preparation by oxidative dehydrogenation of propane, preparation method thereof and propylene preparation method |
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 |