CN114100633B - Catalyst for preparing hydrogen by catalyzing and decomposing hydrogen sulfide by visible light and preparation method thereof - Google Patents
Catalyst for preparing hydrogen by catalyzing and decomposing hydrogen sulfide by visible light and preparation method thereof Download PDFInfo
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- CN114100633B CN114100633B CN202010900126.XA CN202010900126A CN114100633B CN 114100633 B CN114100633 B CN 114100633B CN 202010900126 A CN202010900126 A CN 202010900126A CN 114100633 B CN114100633 B CN 114100633B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 26
- 239000001257 hydrogen Substances 0.000 title claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical group [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
- 229910002367 SrTiO Inorganic materials 0.000 claims description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- 229910017771 LaFeO Inorganic materials 0.000 claims description 2
- 241000627951 Osteobrama cotio Species 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 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
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims 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 claims 4
- 238000000034 method Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6484—Niobium
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6486—Tantalum
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0495—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by dissociation of hydrogen sulfide into the elements
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention relates to a catalyst for preparing hydrogen by catalyzing and decomposing hydrogen sulfide by using visible light and a preparation method thereof, belonging to the technical field of catalyzing and decomposing hydrogen sulfide by using visible light. The catalyst for preparing hydrogen by catalyzing and decomposing hydrogen sulfide through visible light has a structure in a A@B form, wherein A is a metal sulfide, and B is a perovskite oxide. The catalyst for preparing hydrogen by catalyzing and decomposing hydrogen sulfide by using visible light greatly improves the photocatalytic decomposition of H 2 S efficiency, can obtain clean energy H 2 Realize H 2 S is efficiently and cleanly utilized, and almost zero energy consumption is generated in the treatment process; the invention also provides a simple and easy preparation method.
Description
Technical Field
The invention relates to a catalyst for preparing hydrogen by catalyzing and decomposing hydrogen sulfide by using visible light and a preparation method thereof, belonging to the technical field of catalyzing and decomposing hydrogen sulfide by using visible light.
Background
A large amount of H can be generated in the petrochemical and coal chemical production processes 2 S，H 2 S is a chemical that is extremely harmful to the environment and human health. Industrial treatment H 2 The main mode of S is to adopt Claus technology, and the technology has a series of problems of high process energy consumption, secondary pollution caused by generated harmful substances, waste of hydrogen resources caused by hydrogen atoms to generate water and the like.
Decomposition of H by photocatalytic technique 2 S, can recycle H 2 The hydrogen in S realizes 100% utilization of atoms, and can utilize solar energy resources, so that solar energy can be collected and stored in the form of fuel hydrogen, the win-win goal of reducing energy consumption and avoiding environmental pollution is realized, and compared with other H 2 S has obvious advantages.
Currently, the photocatalytic decomposition of H is mostly carried out 2 The catalyst for S hydrogen production adopts ultraviolet light as a light source, and has less application to the field of visible light. Chinese patent CN1978054 and CN01618329 disclose the use of visible light to catalyze and decompose H 2 The method for preparing hydrogen by S has the disadvantages that the catalyst is relatively weak under visible light and the hydrogen production rate of the catalyst is low, and the requirement of practical industrial application cannot be met.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects in the prior art and providing the catalyst for preparing the hydrogen by catalyzing and decomposing hydrogen sulfide by using visible light, which greatly improves the photocatalytic and decomposition of H 2 S efficiency, can obtain clean energy H 2 Realize H 2 The S is used in a high-efficiency cleaning way,and the treatment process has almost zero energy consumption; the invention also provides a simple and easy preparation method.
The catalyst for preparing hydrogen by catalyzing and decomposing hydrogen sulfide through visible light has a structure in a A@B form, wherein A is a metal sulfide, and B is a perovskite oxide.
Preferably, the metal sulfide is MnS, cuS, in 2 S 3 CdS or Bi 2 S 3 。
Preferably, the perovskite oxide is SrTiO 3 、BaTiO 3 、NiTiO 3 、CoTiO 3 、FeTiO 3 、NaTaO 3 、AgTaO 3 、KTaO 3 、AgNbO 3 、CuNbO 3 、LaFeO 3 Or BiFeO 3 。
The preparation method of the catalyst for preparing hydrogen by catalyzing and decomposing hydrogen sulfide by using visible light comprises the following steps:
(1) Dripping a metal precursor into a citric acid aqueous solution to prepare a solution M1;
(2) After stirring for 30min, dropwise adding the metal nitrate aqueous solution into the M1 aqueous solution to obtain a solution M2;
(3) Stirring M2 for 30min, heating to 80 ℃, gradually forming gel by the solution under strong stirring, drying the gel overnight, and roasting to obtain perovskite oxide;
(4) Pouring the prepared perovskite oxide, metal nitrate, thioacetamide and pyridine solution into a high-pressure reaction kettle taking polytetrafluoroethylene as an inner container together, and preserving heat for 18-36h at 180 ℃;
(5) And (3) after the reaction in the step (4), naturally cooling to room temperature, filtering and washing the obtained solid sample by adopting ethanol, and drying after the washing is finished, thus obtaining a series of different sulfide metal salt@perovskite heterojunction catalysts.
In step (1), the metal precursor is preferably tetrabutyl titanate, n-thallium acid ester, niobium nitrate or iron nitrate.
In step (2), the metal nitrate is preferably strontium nitrate, barium nitrate, nickel nitrate, iron nitrate, sodium nitrate, silver nitrate, potassium nitrate, copper nitrate, lanthanum nitrate or bismuth nitrate.
In the step (3), the drying temperature is 60-120 ℃; the roasting temperature is 500-1000 ℃.
In the step (4), the metal nitrate is preferably manganese nitrate, copper nitrate, indium nitrate, cadmium nitrate or bismuth nitrate; preserving heat for 18-36h at 180 ℃.
In the step (5), the drying temperature is 50-100 ℃.
In the catalyst prepared in the step (5), the mass ratio of the metal sulfide is 5-60%.
The metal sulfide has narrower forbidden band and better light absorption property, and is the most commonly used photocatalytic decomposition H at present 2 S catalyst, in particular for decomposing H under visible light conditions 2 The performance of S is particularly outstanding; ABO (anaerobic-anoxic-oxic) 3 Perovskite metal oxides are a semiconductor material with excellent properties and wide application, are considered as a photocatalyst with the most application prospect, and are widely applied to a plurality of photocatalysis fields. The invention combines two semiconductor materials with different forbidden bandwidths to form the heterojunction, can realize the advantage complementation of the two semiconductors, and is an important way for expanding the spectral response range of the catalyst, improving the electron and hole analysis efficiency and effectively improving the reaction performance of the photocatalyst.
The heterojunction catalyst is formed by adopting a mode of compounding metal sulfide and perovskite and is used for decomposing H under the condition of visible light 2 S, thus effectively avoiding the conventional treatment H 2 S, the technology has high energy consumption and the tail gas is still polluted; at the same time H can also be 2 S is decomposed into H 2 And sulfur, realize H 2 S is utilized efficiently. Catalytic decomposition of H under conventional visible light conditions 2 S has lower process efficiency, and the invention adopts a mode of compounding metal sulfide and perovskite materials to synthesize the metal sulfide@perovskite heterojunction catalyst which can efficiently decompose H under the condition of visible light 2 S prepares hydrogen to realize zero energy consumption decomposition H 2 S。
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts the metal sulfide and perovskite to be compounded to form the heterojunction catalyst,the characteristics of strong light absorption performance of metal sulfide and high responsiveness of perovskite oxide under the condition of visible light are fully utilized, and the combination of the advantages of the two catalysts is realized, so that H can be efficiently carried out under the condition of visible light 2 S is decomposed into H 2 And elemental S;
(2) When the catalyst prepared by the invention is used for preparing hydrogen by catalyzing and decomposing hydrogen sulfide by using visible light, H is treated efficiently 2 S pollutant and clean energy H can be obtained 2 Realize H 2 S is efficiently and cleanly utilized, and almost zero energy consumption is generated in the treatment process.
Detailed Description
The invention is further illustrated below in connection with examples, which are not intended to limit the practice of the invention.
Example 1
Dripping 0.1mol of tetrabutyl titanate into a citric acid aqueous solution to prepare a solution M1, stirring for 30min, dripping 0.1mol of strontium nitrate aqueous solution into the M1 aqueous solution to obtain a solution M2, stirring for 30min, heating to 80 ℃, gradually forming gel under strong stirring, drying the gel at 120 ℃, and roasting at 750 ℃ to prepare SrTiO 3 Perovskite oxide.
0.8g of SrTiO prepared 3 Pouring the mixture into a high-pressure reaction kettle taking polytetrafluoroethylene as an inner container together with 0.4g of manganese nitrate, 0.8g of thioacetamide and 50ml of pyridine solution, preserving the temperature for 18 hours at 180 ℃, naturally cooling to room temperature after the reaction is finished, filtering and washing the obtained solid sample by ethanol, and drying at 60 ℃ after the washing is finished to obtain MnS@SrTiO with the MnS content of 20% 3 Heterojunction catalysts.
Example 2
Dripping 0.1mol of tetrabutyl titanate into a citric acid aqueous solution to prepare a solution M1, stirring for 30min, dripping 0.1mol of barium nitrate aqueous solution into the M1 aqueous solution to obtain a solution M2, stirring for 30min, heating to 80 ℃, gradually forming gel under strong stirring, drying the gel at 100 ℃, and roasting at 850 ℃ to prepare BaTiO 3 Perovskite oxide.
0.7g of the prepared BaTiO 3 Pouring the mixture into a high-pressure reaction kettle taking polytetrafluoroethylene as an inner container together with 0.6g of copper nitrate, 2.4g of thioacetamide and 50ml of pyridine solution, preserving the temperature for 24 hours at 180 ℃, naturally cooling to room temperature after the reaction is finished, filtering and washing the obtained solid sample by adopting ethanol, and drying at 80 ℃ after the washing is finished to obtain CuS@BaTiO with 30% CuS content 3 Heterojunction catalysts.
Example 3
Dripping 0.1mol of normal thallium acid ester into a citric acid aqueous solution to prepare a solution M1, stirring for 30min, dripping 0.1mol of silver nitrate aqueous solution into the M1 aqueous solution to obtain a solution M2, stirring for 30min, heating to 80 ℃, gradually forming gel by strong stirring, drying the gel at 80 ℃, and roasting at 950 ℃ to prepare AgTaO 3 Perovskite oxide.
0.6g of AgTaO prepared 3 Pouring the mixture into a high-pressure reaction kettle taking polytetrafluoroethylene as an inner container together with 0.8g of indium nitrate, 3.2g of thioacetamide and 50ml of pyridine solution, preserving the temperature for 30 hours at 180 ℃, naturally cooling to room temperature after the reaction is finished, filtering and washing the obtained solid sample by adopting ethanol, and drying at 60 ℃ after the washing is finished to obtain In 2 S 3 In content of 40% 2 S 3 @AgTaO 3 Heterojunction catalysts.
Example 4
Dripping 0.1mol of niobium nitrate into aqueous solution of citric acid to obtain solution M1, stirring for 30min, dripping 0.1mol of aqueous solution of silver nitrate into aqueous solution M1 to obtain solution M2, stirring for 30min, heating to 80 ℃, gradually forming gel under strong stirring, drying the gel at 110 ℃, and roasting at 650 ℃ to obtain AgNbO 3 Perovskite oxide.
0.5g of AgNbO prepared 3 Pouring the mixture into a high-pressure reaction kettle taking polytetrafluoroethylene as an inner container together with 1g of bismuth nitrate, 4.0g of thioacetamide and 50ml of pyridine solution, preserving the temperature for 36 hours at 180 ℃, naturally cooling to room temperature after the reaction is finished, filtering and washing the obtained solid sample by adopting ethanol, and drying at 70 ℃ after the washing is finished to obtain Bi 2 S 3 Bi content of 50% 2 S 3 @AgNbO 3 Heterojunction catalysts.
Comparative example 1
Dripping 0.1mol of tetrabutyl titanate into a citric acid aqueous solution to prepare a solution M1, stirring for 30min, dripping 0.1mol of strontium nitrate aqueous solution into the M1 aqueous solution to obtain a solution M2, stirring for 30min, heating to 80 ℃, gradually forming gel under strong stirring, drying the gel at 120 ℃, and roasting at 750 ℃ to prepare SrTiO 3 Perovskite oxide.
Comparative example 2
And (3) pouring 0.5g of manganese nitrate, 1g of thioacetamide and 50ml of pyridine solution into a high-pressure reaction kettle taking polytetrafluoroethylene as an inner container, preserving heat for 18 hours at 180 ℃, naturally cooling to room temperature after the reaction is finished, filtering and washing the obtained solid sample by adopting ethanol, and drying at 60 ℃ after the washing is finished to obtain a series of different MnS.
Catalyst evaluation process:
will H 2 S gas is continuously introduced into a reactor of a photocatalysis evaluation device provided with a specific organic solvent and a photocatalyst, 50 milligrams of catalyst is added, the gas flow is 10ml/min, the system is evacuated and then is subjected to illumination by a xenon lamp, the light source intensity is 300W, a certain reaction temperature is controlled, and the generated hydrogen is subjected to online detection by gas chromatography, wherein the detection result is shown in table 1.
TABLE 1
| Catalyst | Hydrogen production activity (mmol/h) |
| Example 1 | 20 |
| Example 2 | 15 |
| Example 3 | 16 |
| Example 4 | 18 |
| Comparative example 1 | 2 |
| Comparative example 2 | 1 |
Claims (6)
1. The application of the catalyst with A@B structure in preparing hydrogen by catalyzing and decomposing hydrogen sulfide by visible light is characterized in that: the catalyst has a structure in the form of A@B, wherein A is a metal sulfide and B is a perovskite oxide;
metal sulfide MnS, cuS, in 2 S 3 CdS or Bi 2 S 3 ；
The perovskite oxide is SrTiO 3 、BaTiO 3 、NiTiO 3 、CoTiO 3 、FeTiO 3 、NaTaO 3 、AgTaO 3 、KTaO 3 、AgNbO 3 、CuNbO 3 、LaFeO 3 Or BiFeO 3 ；
The mass ratio of the metal sulfide is 5-60%;
the preparation method of the catalyst comprises the following steps:
(1) Dripping a metal precursor into a citric acid aqueous solution to prepare a solution M1;
(2) After stirring, dropwise adding a metal nitrate aqueous solution into the M1 aqueous solution to obtain a solution M2;
(3) Stirring M2, heating, gradually forming gel by the solution under stirring, drying the gel overnight, and roasting to obtain perovskite oxide;
(4) Pouring the prepared perovskite oxide, metal nitrate, thioacetamide and pyridine solution into a high-pressure reaction kettle taking polytetrafluoroethylene as an inner container together, and preserving heat at 180 ℃ for 18-36h;
(5) And (3) after the reaction in the step (4), naturally cooling to room temperature, filtering and washing the obtained solid sample by adopting ethanol, and drying after the washing is finished, thus obtaining a series of different sulfide metal salt@perovskite heterojunction catalysts.
2. The use of the catalyst of structure A@B in the catalytic decomposition of hydrogen sulfide to produce hydrogen in visible light according to claim 1, wherein: in the step (1), the metal precursor is tetrabutyl titanate, n-thallium acid ester, niobium nitrate or ferric nitrate.
3. The use of the catalyst of structure A@B in the catalytic decomposition of hydrogen sulfide to produce hydrogen in visible light according to claim 1, wherein: in the step (2), the metal nitrate is strontium nitrate, barium nitrate, nickel nitrate, ferric nitrate, sodium nitrate, silver nitrate, potassium nitrate, copper nitrate, lanthanum nitrate or bismuth nitrate.
4. The use of the catalyst of structure A@B in the catalytic decomposition of hydrogen sulfide to produce hydrogen in visible light according to claim 1, wherein: in the step (3), the drying temperature is 60-120 ℃; the roasting temperature is 500-1000 ℃.
5. The use of the catalyst of structure A@B in the catalytic decomposition of hydrogen sulfide to produce hydrogen in visible light according to claim 1, wherein: in the step (4), the metal nitrate is manganese nitrate, copper nitrate, indium nitrate, cadmium nitrate or bismuth nitrate; preserving heat at 180 ℃ for 18-36h.
6. The use of the catalyst of structure A@B in the catalytic decomposition of hydrogen sulfide to produce hydrogen in visible light according to claim 1, wherein: in the step (5), the drying temperature is 50-100 ℃.
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