CN115007147B - Photocatalytic composite material and preparation method thereof - Google Patents
Photocatalytic composite material and preparation method thereof Download PDFInfo
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- CN115007147B CN115007147B CN202210643455.XA CN202210643455A CN115007147B CN 115007147 B CN115007147 B CN 115007147B CN 202210643455 A CN202210643455 A CN 202210643455A CN 115007147 B CN115007147 B CN 115007147B
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 49
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052802 copper Inorganic materials 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000004108 freeze drying Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000010936 titanium Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 229910017566 Cu-Mn Inorganic materials 0.000 claims abstract description 12
- 229910017871 Cu—Mn Inorganic materials 0.000 claims abstract description 12
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 9
- 230000008961 swelling Effects 0.000 claims abstract description 8
- 239000000839 emulsion Substances 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 11
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 9
- 238000010335 hydrothermal treatment Methods 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 238000007146 photocatalysis Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 42
- 239000001569 carbon dioxide Substances 0.000 abstract description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 230000009467 reduction Effects 0.000 abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052719 titanium Inorganic materials 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 239000000243 solution Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 15
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 229910000431 copper oxide Inorganic materials 0.000 description 11
- 239000005751 Copper oxide Substances 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 229920005654 Sephadex Polymers 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000012507 Sephadex™ Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- QTZWARTZYFQYKD-UHFFFAOYSA-N [Ti].[Cu].[Mn] Chemical compound [Ti].[Cu].[Mn] QTZWARTZYFQYKD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 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
- 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
- B01J23/72—Copper
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/61—
-
- 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
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/087—Photocatalytic compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
-
- 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
Abstract
The invention belongs to the field of catalytic materials, and particularly relates to a photocatalytic composite material and a preparation method thereof. The method comprises the following steps: 1) Soaking the Gel into copper liquid for swelling and freeze-drying, and then placing the Gel into manganese copper liquid for sequential hydrothermal and freeze-drying to obtain a Gel-Cu-Mn template; 2) Immersing the Gel-Cu-Mn template in a titanyl sulfate solution until the solution becomes white emulsion and becomes clear, and then completing Ti loading to obtain a Gel-Cu-Mn-Ti precursor, and performing freeze drying, crushing and sieving to obtain precursor powder; 3) And (3) placing the precursor powder in a protective atmosphere for heat treatment, and obtaining the photocatalytic composite material after the heat treatment is completed. The copper, manganese and titanium in the photocatalytic material realize effective compounding, and produce synergistic effect, so that the copper has the capability of efficiently and continuously photocatalytic conversion and reduction of carbon dioxide, and has longer service life.
Description
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to a photocatalytic composite material and a preparation method thereof.
Background
CuO is a typical photocatalytic active material that is capable of being exposed to lightEffectively CO in aqueous solution 2 Reduction to organic matter is widely used in the field of photoelectrocatalysis. However, due to its conduction band potential covering its self-reduction potential, it is involved in the photoelectrocatalytic reduction of CO 2 The material is reduced, the conversion efficiency is low, the material needs to be covered with other semiconductor materials, and an n-type semiconductor is covered on the material to prepare a composite electrode for photoelectrocatalysis, so that efficient photoelectrocatalysis CO conversion is generated 2 Is effective in (1). But also thus greatly limits its application.
For this reason, researchers have been developing from different angles in order to improve the photocatalytic effect of CuO. MOFs are commonly used to form metal-organic framework materials, typically the MOF-5, uiO-66 and MIL-125 families. However, modification of the optical energy groups of MOFs is complicated, and practical stability and the like of the MOFs are effective, so that the MOFs are difficult to store. Therefore, the application effect is limited in practical industrial or environmental protection application, and the inorganic photocatalytic material is still the optimal photocatalytic active material selection.
Disclosure of Invention
The invention provides a photocatalytic composite material and a preparation method thereof, aiming at solving the problems that the actual light conversion efficiency of the existing inorganic photocatalytic material is low, carbon dioxide reduction is required to be carried out by an electrode in a photoelectrocatalysis mode, the reduction efficiency is low, and the effective regeneration cannot be carried out.
The invention aims at:
1. the photocatalytic conversion effect of the Cu-based catalytic material on carbon dioxide is effectively improved;
2. so that the photocatalytic material has good reproducibility in practice;
3. the application field of the photocatalytic material is improved, so that the photocatalytic material has wide application prospect.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
A preparation method of a photocatalysis composite material,
the method comprises the following steps:
1) Immersing the Gel serving as a template into copper liquid, standing for swelling, then freeze-drying, placing the template into manganese copper liquid for hydrothermal treatment after freeze-drying, and freeze-drying again to obtain a Gel-Cu-Mn template;
2) Placing the Gel-Cu-Mn template in a titanium oxysulfate solution, carrying out low-temperature impregnation, slowly heating and/or preserving heat in the impregnation process until the solution becomes white emulsion, and then clarifying to finish Ti loading, thus obtaining a Gel-Cu-Mn-Ti precursor, washing the Gel-Cu-Mn-Ti precursor, then carrying out freeze drying again, crushing and sieving to obtain precursor powder;
3) And (3) placing the precursor powder in a protective atmosphere for heat treatment, and obtaining the photocatalytic composite material after the heat treatment is completed.
In the scheme of the invention, gel is used as a template, a template method is adopted to improve the specific surface area of the product, and compared with a conventional hydrothermal method or electrodeposition method, the template method is adopted for in-situ growth preparation, so that the product with a specific microstructure and high specific surface area can be obtained most effectively. Meanwhile, in the preparation method, copper oxide is used as a target product to form manganese and titanium oxide for cooperation, so that the material activity of the copper oxide under the photocatalysis condition is improved.
This is because titanium dioxide and manganese dioxide are both photocatalytic materials themselves, which have photocatalytic activity. Although the titanium dioxide does not have actual carbon dioxide conversion activity, as the titanium dioxide can absorb the energy of photoelectrons in the environment, electrons of the titanium dioxide are excited to a conduction band, valence band holes are left to form photo-generated electron hole pairs, meanwhile, anion free radicals are generated to excite manganese dioxide, manganese oxide has a certain oxidizing property to promote the oxidation and regeneration of copper oxide after receiving the free radicals, and the continuous autogenous catalytic reduction of carbon dioxide to produce methanol is realized, on the other hand, the manganese oxide can release energy while oxidizing and regenerating the copper oxide, so that the catalytic conversion effect of the copper oxide on the carbon dioxide is further promoted, and the photocatalytic activity of the copper oxide is improved.
Therefore, the synergistic effect of the three is very remarkable, but the actual proportioning amount of the three needs to be strictly controlled, otherwise, the situation that the formaldehyde obtained by reducing the copper oxide by manganese oxide is oxidized by manganese oxide easily occurs, so that the actual photocatalytic activity is inhibited.
As a preferred alternative to this,
the gel in the step 1) is crosslinked glucose gel.
Sephadex, which is widely used for desalination, i.e. it has good ion adsorption, is commercially available under the name Sephadex. For the sephadex, the G-10, G15, G-25 and G-50 gel is selected optimally, the cost is relatively low, the desalting effect is excellent, and other organic impurities are not easy to introduce. Meanwhile, the gel pores are larger, and if the cross-linked dextran gel with the cross-linking degree of G-75 and more than 75 is adopted, the specific surface area of the obtained product is found to be smaller in the actual preparation process, and the load of titanium is smaller, so that the actual catalytic activity is weakened.
As a preferred alternative to this,
step 1) the copper liquid is cuprous solution;
the cuprous solution contains 0.12-0.18 mol/L cuprous ions and 1.5-3.0 mol/L hydrogen chloride;
and selectively adding elemental copper when immersing the template into copper liquid for standing and swelling.
The invention selects cuprous solution and adds simple substance copper, which is a series of linkage effect for disproportionation and normalization. The cuprous ions are bad in chemical stability, disproportionation can be continuously generated in an acidic environment, and under the action of the simple substance copper, the cupric ions and the simple substance copper can continuously form monovalent copper ions, so that copper and divalent copper can be loaded on the template in a penetrating way. The method solves the problem that simple substance copper is difficult to directly and effectively carry out deposition load and growth, realizes doping of copper and bivalent copper, continuously refines growing crystal grains, and finally the obtained product has obvious improvement effect on catalytic activity.
As a preferred alternative to this,
and step 1), the freeze drying process is carried out until the thickness of the material is reduced to 40-60% of the original thickness.
In the thinning process, a large number of crystal defects such as grain boundaries, lattice dislocation and the like are generated due to internal deformation, so that grown loads can be increased to form a substructure inside a crystal, further, the transformation of a rich bicrystal structure/polycrystalline structure is realized, unsaturated coordination sites caused by the high lattice disorder of the bicrystal structure/polycrystalline structure are increased, and the improvement of catalytic activity and selectivity is realized. Originally, the conversion efficiency is low due to the mass transfer limitation of carbon dioxide and carbon monoxide and HER reaction, and the original copper oxide has no obvious tendency of dislocation, twin crystal, defect accumulation and the like in the nucleation and growth processes, so that the phenomenon can be remarkably synergistically enhanced by realizing defect accumulation in the proper disproportionation and proper freeze drying.
As a preferred alternative to this,
the manganese-copper liquid in the step 1) contains 0.25-0.35 mol/L copper ions and 0.13-0.30 mol/L manganese;
the manganese is +4 valent and/or +5 valent and/or +6 valent and/or +7 valent, and at least contains any one of +6 valent and +7 valent manganese, and the content of +6 valent and +7 valent manganese ions should be at least 0.1mol/L.
In the technical scheme of the invention, the dosage ratio of manganese to copper needs to be strictly controlled so as not to lead to the fact that an actual product cannot catalyze reduction and conversion of carbon dioxide into organic matters, but rather, the serious problem of oxidizing the organic matters into carbon dioxide can occur. In addition, the relative content of copper oxide can be increased by taking high-valence manganese ions as main raw materials, so that the actual photocatalytic effect is improved.
In addition, the purpose of selecting high valence manganese is to realize the conversion of cuprous and metallic copper and improve the relative content of cupric so as to ensure that the content of active ingredients is higher, and the high valence manganese can be spontaneously reduced into manganese oxide in the actual subsequent heat treatment process, so that the high valence manganese has the capability of self-adaptive conversion, and the low valence manganese is easy to cause the problem that the content of active ingredients is reduced and the quality of the whole product cannot be stably ensured.
As a preferred alternative to this,
the reaction temperature of the hydrothermal treatment in the step 1) is 120-180 ℃, and the reaction time is 11-13 h.
In the above reaction time and temperature ranges, a relatively optimal treatment effect can be produced. Because the hydrothermal treatment can significantly affect the nucleation and growth tendencies of copper and manganese, resulting in a more varied effect.
As a preferred alternative to this,
in the titanyl sulfate solution in the step 2), the concentration of titanyl sulfate is 0.15-0.25 mol/L, and the pH value is regulated to 4-6;
the titanyl sulfate solution is prepared in ice water bath.
Because of the relatively poor chemical stability of titanyl sulfate itself, it is desirable to more tightly control the formulation conditions of the titanyl sulfate solution.
As a preferred alternative to this,
step 2), the initial temperature of the low-temperature impregnation is 4-8 ℃;
and in the soaking process, the temperature is slowly increased at the temperature increasing speed of 6 ℃/h, and the temperature is maintained after the temperature is increased to be more than or equal to 65 ℃.
The impregnation is started at a low temperature, so that the actual damage and blockage of the porous structure of the original intermediate caused by dense precipitation and deposition of titanium dioxide can be avoided, and the reduction of the porosity and the specific surface area of the porous structure can be avoided.
As a preferred alternative to this,
the heat treatment in step 3) is as follows: heating to 330-380 ℃ and preserving heat for 2-3 h, then heating to 550-650 ℃ and preserving heat for 2-3 h, and cooling along with the furnace.
Under the heat treatment condition, the combination and conversion of each metal oxide can be effectively realized, the gel is carbonized by forming, the actual copper-manganese-titanium synergistic effect is improved, and the electron conduction capacity in the material is improved.
A photocatalytic composite material.
The photocatalytic composite material can be realized under the condition of single light irradiation in a very limited way, can realize the effective photocatalytic conversion of carbon dioxide to produce methanol without electrifying, has high material stability and strong reproducibility, and has relatively extremely long service life.
The excellent effects of the invention are as follows:
1) The preparation method is simple and efficient, and can rapidly and effectively realize the catalytic active material with a multi-level polycrystalline structure;
2) Copper, manganese and titanium realize effective compounding, and produce synergistic effect, so that the copper has the capability of efficiently and continuously carrying out photocatalytic conversion and reduction on carbon dioxide, and has longer service life;
3) The conversion selectivity is strong and the effect is stable.
Drawings
FIG. 1 is a graph showing the average result of the carbon dioxide catalytic conversion test of examples 1 to 3;
FIG. 2 is a graph showing the results of the life test of the photocatalytic activity in example 6.
Detailed Description
The invention is described in further detail below with reference to specific examples and figures of the specification. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
The raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art unless specifically stated otherwise; the methods used in the examples of the present invention are those known to those skilled in the art unless specifically stated otherwise.
Example1
A preparation method of the photocatalytic composite material comprises the following steps:
1) Immersing a Sephadex G-25 Gel serving as a template into copper liquid, standing and swelling for 2 hours, wherein the copper liquid contains 0.15mol/L copper chloride and 2.0mol/L hydrogen chloride, adding metal copper in a proportion of adding 5G of elemental copper into each liter of copper liquid, then freeze-drying, placing the copper liquid into manganese copper liquid until the copper liquid reaches 50% of the original thickness, performing 150 ℃ hydrothermal treatment for 12 hours, and performing freeze-drying again for 60 minutes to obtain a Gel-Cu-Mn template;
2) Placing the Gel-Cu-Mn template in a titanium oxysulfate solution, preparing the titanium oxysulfate in an ice-water bath, carrying out ultrasonic vibration dissolution for 2min, adjusting the pH value to 4 by dilute sulfuric acid, starting soaking at 6 ℃, slowly heating to 65 ℃ at the speed of 6 ℃/h, preserving heat until the solution turns into white emulsion, standing until Ti loading is completed after clarification, obtaining a Gel-Cu-Mn-Ti precursor, washing the Gel-Cu-Mn-Ti precursor, carrying out freeze drying for 12h again, crushing, and sieving by a 2mm sieve to obtain precursor powder;
3) And (3) heating the precursor powder to 350 ℃ in a nitrogen atmosphere, preserving heat for 2 hours, then heating to 620 ℃ and preserving heat for 3 hours, cooling along with a furnace, and obtaining the photocatalytic composite material after heat treatment is completed.
Example 2
A preparation method of the photocatalytic composite material comprises the following steps:
1) Immersing a Sephadex G-25 Gel serving as a template into copper liquid, standing and swelling for 2 hours, wherein the copper liquid contains 0.12mol/L copper chloride and 1.5mol/L hydrogen chloride, adding metal copper in a proportion of adding 5G of elemental copper into each liter of copper liquid, then freeze-drying, placing the copper liquid into manganese copper liquid until the copper liquid reaches 40% of the original thickness, performing 120 ℃ hydrothermal treatment for 13 hours, and performing freeze-drying again for 45 minutes to obtain a Gel-Cu-Mn template;
2) Placing the Gel-Cu-Mn template in a titanium oxysulfate solution, preparing the titanium oxysulfate in an ice-water bath, carrying out ultrasonic vibration dissolution for 2min, adjusting the pH value to 4 by dilute sulfuric acid, starting soaking at 8 ℃, slowly heating to 65 ℃ at a speed of 6 ℃/h, preserving heat until the solution turns into white emulsion, standing until Ti loading is completed after clarification, obtaining a Gel-Cu-Mn-Ti precursor, washing the Gel-Cu-Mn-Ti precursor, carrying out freeze drying for 12h again, crushing, and sieving by a 2mm sieve to obtain precursor powder;
3) And (3) heating the precursor powder to 330 ℃ in nitrogen atmosphere and preserving heat for 2 hours, then heating to 650 ℃ and preserving heat for 3 hours, cooling along with a furnace, and obtaining the photocatalytic composite material after heat treatment is completed.
Example 3
A preparation method of the photocatalytic composite material comprises the following steps:
1) Immersing a Sephadex G-25 Gel serving as a template into copper liquid, standing and swelling for 2 hours, wherein the copper liquid contains 0.18mol/L copper chloride and 3.0mol/L hydrogen chloride, adding metal copper in a proportion of adding 5G of elemental copper into each liter of copper liquid, then freeze-drying, placing the copper liquid into manganese copper liquid until the copper liquid reaches 60% of the original thickness, performing 180 ℃ hydrothermal treatment for 11 hours, and performing freeze-drying again for 60 minutes to obtain a Gel-Cu-Mn template;
2) Placing the Gel-Cu-Mn template in a titanium oxysulfate solution, preparing the titanium oxysulfate in an ice-water bath, carrying out ultrasonic vibration dissolution for 2min, adjusting the pH value to 4 by dilute sulfuric acid, starting soaking at the temperature of 4 ℃, slowly heating to 65 ℃ at the speed of 6 ℃/h, preserving heat until the solution turns into white emulsion, standing until Ti loading is completed after clarification, obtaining a Gel-Cu-Mn-Ti precursor, washing the Gel-Cu-Mn-Ti precursor, carrying out freeze drying for 12h again, crushing, and sieving by a 2mm sieve to obtain precursor powder;
3) And (3) heating the precursor powder to 380 ℃ in a nitrogen atmosphere, preserving heat for 3 hours, then heating to 550 ℃ and preserving heat for 2 hours, cooling along with a furnace, and obtaining the photocatalytic composite material after heat treatment is completed.
Photocatalytic Performance efficiency test
The photocatalytic composite materials prepared in examples 1 to 3 were subjected to carbon dioxide catalytic conversion performance test.
Placing the prepared powder of the photocatalysis composite material into 0.05mol/L sodium bicarbonate solution, adding the photocatalysis composite material in a proportion of 20g per liter of sodium bicarbonate solution, continuously blowing carbon dioxide into the powder, continuously blowing the gas for 15min, and then opening a xenon lamp to adjust the illumination energy density to 380mw/cm 2 The irradiation was for 10min and the sampling test record was made of methanol production per minute. As particularly shown in fig. 1. Methanol production units μmol/10g corresponds to the minute production per 10g of photocatalyst composite. Examples 1 to 3 are labeled examples 1 to 3, respectively.
As is apparent from the data of FIG. 1, the photocatalytic material prepared by the present invention has the advantages of rapid excitation and high purityThe nature of the effective conversion is somewhat lower than that of the electrode-form photoelectrocatalytic material, although the actual conversion efficiency is somewhat lower (typically the electrode-form photoelectrocatalytic material has a conversion efficiency of about 185. Mu. Mol/cm 2 ) But the practical application value is remarkably improved. The invention can realize the photocatalytic conversion of carbon dioxide without electrifying, is more convenient to use, can effectively reduce the preparation cost and the equipment requirement when being used for producing methanol in the photocatalytic industry, has simple and efficient operation, and can only need to continuously blow air and provide illumination.
Furthermore, comparing the data of examples 1-3 in FIG. 1, it can be seen that example 2 has relatively the highest conversion stability with less fluctuation of conversion efficiency, but the difference between the three is not significant.
Photocatalytic Activity Life test
Placing the prepared powder of the photocatalysis composite material into 0.05mol/L sodium bicarbonate solution, adding the photocatalysis composite material in a proportion of 20g per liter of sodium bicarbonate solution, continuously blowing carbon dioxide into the powder, continuously blowing the gas for 15min, and then opening a xenon lamp to adjust the illumination energy density to 380mw/cm 2 The methanol yield per minute was recorded by sampling and detection, and after the methanol yield was less than or equal to 100. Mu. Mol/10g, the test results were shown in the following table.
| Example1 | Example 2 | Example 3 | |
| Service life per day | 63 | 61 | 58 |
Compared with the conventional photoelectric composite catalytic electrode, the service life of the photocatalytic material is about 30d, and the service life of the photocatalytic material can be prolonged by more than one time.
After the test, after the sun-drying exposure is carried out for 7 days, the photocatalytic conversion performance of the solar energy collector can be recovered to at least 95% of the original photocatalytic conversion performance, the solar energy collector has very strong reproducibility, or the irradiation power of a xenon lamp is increased, and although the conversion efficiency is not obviously improved, the service life of the solar energy collector can be obviously prolonged.
The regenerability is mainly characterized in that oxides of manganese and titanium can generate a large amount of superoxide anion free radicals under the condition of solar insolation, so that copper or cuprous oxide which is reduced to cause failure is further effectively oxidized into copper oxide, and the activity of reducing and converting carbon dioxide is recovered.
Example 4
Based on example1, the same photocatalytic performance efficiency test as described above was performed, except that the gel selection was replaced, as in example 1. The test results are shown in the following table.
As can be seen from the test results of the table, the practical gel has a great influence on the product performance of the technical scheme of the invention, especially the Sephadex G-100 gel, has extremely poor actual subsequent titanium loading effect along with the increase of the crosslinking degree, obviously reduces the conversion efficiency and the excitation efficiency, and according to the practical test results, the ultimate conversion efficiency is only about 94-96 mu mol/10G, and meanwhile, the practical service life is reduced to about 60% of the maximum average conversion amount and is recorded as scrapped, and the practical service life is only about 20d, so that the practical service life is greatly shortened, and the reproducibility is also obviously weakened.
Example 5
Based on example1, the same photocatalytic performance efficiency test as described above was performed, except that the composition of the manganese copper liquid was adjusted, as in example 1. The test results are shown in the following table.
The detection test results show that the proportion of the manganese-copper liquid has a very critical effect on the performance of the product, the relative content of manganese is increased, the rapid activation of catalytic conversion can be realized very effectively, but along with the improvement of the content of manganese, the conversion efficiency of methanol is obviously reduced in practice, and even the conversion of methanol cannot be realized completely. This is because manganese oxide has the capability of oxidizing and catalytically converting organic matters under the photocatalytic condition, and manganese oxide is also used as a photocatalytic active material for catalytic degradation of formaldehyde, so that the content ratio of copper to manganese is a very critical factor affecting the performance for the technical scheme of the invention.
Example 6
Based on example1, the same photocatalytic performance efficiency test as described above was performed, except that the components of the titanyl sulfate solution were adjusted as in example 1. The test results are shown in the following table.
From the test results in the table, it can be seen that the concentration of the titanyl sulfate solution is adjusted within a certain range, and the conversion efficiency of the product is relatively less affected.
However, further carrying out a photo-catalytic activity life test, recording the day data by taking the average value of daily detection and measurement on the same day, and recording every 30min by daily detection and measurement, so as to find that the two have completely different catalytic trends. As particularly shown in fig. 2. As is apparent from fig. 2, the change in the concentration of the titanyl sulfate solution actually affects the loading and loading effect thereof, and the effect on the service life of the product is very remarkable. In practice, under the above concentration conditions, an effective load can be achieved without affecting the porosity of the product, as can be seen from the practical short-term conversion efficiency, but in the long term, the primary role of titanium oxide is to cooperate with manganese copper, especially in promoting the regenerative reduction of copper in the catalytic process, so that it has a longer service life, and the experimental group of examples (0.10 mol/L) shows a significant reduction in service life, so that it drops below a conversion rate of 100 μmol/10g, i.e. "scrapped", at about 22 d. However, when the titanium oxysulfate is used in too high a concentration, the conversion is found to be even negative, in the order of 25d, because the methanol content in the solution system is found to be even reduced in the actual detection compared with the previous detection, and after the phenomenon is found, a proper amount of methanol is added into the solution to study the mechanism, and finally the output of the actual carbon dioxide is found to be larger than the bubbling amount, which indicates that the methanol is oxidized into carbon dioxide, thus being recorded as negative. The results show that a relatively high content of actual titanium does not only enable an efficient catalytic conversion of carbon dioxide, but even results in substantial consumption of the methanol already produced.
Therefore, by combining the embodiments and the experiments, the photocatalytic material can effectively realize the catalytic conversion of carbon dioxide under the condition of only illumination and catalysis, and has extremely high industrial utilization value. However, for the technical scheme of the invention, the selection of the gel and the proportion of each component are very critical and important.
Claims (5)
1. A preparation method of a photocatalysis composite material is characterized in that,
the method comprises the following steps:
1) Immersing the Gel serving as a template into copper liquid, standing for swelling, then freeze-drying, placing the template into manganese copper liquid for hydrothermal treatment after freeze-drying, and freeze-drying again to obtain a Gel-Cu-Mn template;
2) Placing the Gel-Cu-Mn template in a titanium oxysulfate solution, carrying out low-temperature impregnation, slowly heating and/or preserving heat in the impregnation process until the solution becomes white emulsion, and then clarifying to finish Ti loading, thus obtaining a Gel-Cu-Mn-Ti precursor, washing the Gel-Cu-Mn-Ti precursor, then carrying out freeze drying again, crushing and sieving to obtain precursor powder;
3) Placing the precursor powder in a protective atmosphere for heat treatment, and obtaining the photocatalytic composite material after the heat treatment is completed;
wherein the gel in the step 1) is crosslinked glucose gel;
step 1) the copper liquid is cuprous solution;
the cuprous solution contains 0.12-0.18 mol/L cuprous ions and 1.5-3.0 mol/L hydrogen chloride;
the template is immersed into copper liquid for standing and swelling, and elemental copper is added;
step 1) the freeze drying process is carried out until the thickness of the material is reduced to 40-60% of the original thickness;
the manganese-copper liquid in the step 1) contains 0.25-0.35 mol/L copper ions and 0.13-0.30 mol/L manganese;
the manganese is +4 valent and/or +5 valent and/or +6 valent and/or +7 valent, and at least contains any one of +6 valent and +7 valent manganese;
the heat treatment in step 3) is as follows: heating to 330-380 ℃ and preserving heat for 2-3 h, then heating to 550-650 ℃ and preserving heat for 2-3 h, and cooling with the furnace.
2. The method for preparing a photocatalytic composite material according to claim 1, characterized in that,
the reaction temperature of the hydrothermal treatment in the step 1) is 120-180 ℃, and the reaction time is 11-13 h.
3. The method for preparing a photocatalytic composite material according to claim 1, characterized in that,
in the titanyl sulfate solution in the step 2), the concentration of titanyl sulfate is 0.15-0.25 mol/L, and the pH value is regulated to 4-6;
the titanyl sulfate solution is prepared in ice water bath.
4. A method for preparing a photocatalytic composite material according to claim 1 or 3, characterized in that,
step 2), the initial temperature of the low-temperature impregnation is 4-8 ℃;
and in the soaking process, the temperature is slowly increased at the temperature increasing speed of 6 ℃/h, and the temperature is maintained after the temperature is increased to be more than or equal to 65 ℃.
5. A photocatalytic composite material obtainable by the process according to any one of claims 1 to 4.
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