CN113731466B - MoC/nitrogen doped carbon/g-C 3 N 4 Composite photocatalyst, preparation and application thereof - Google Patents
MoC/nitrogen doped carbon/g-C 3 N 4 Composite photocatalyst, preparation and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 102
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 126
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 63
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000000137 annealing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- KLOIYEQEVSIOOO-UHFFFAOYSA-N carbocromen Chemical compound CC1=C(CCN(CC)CC)C(=O)OC2=CC(OCC(=O)OCC)=CC=C21 KLOIYEQEVSIOOO-UHFFFAOYSA-N 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000004888 barrier function Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000006479 redox reaction Methods 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 229910039444 MoC Inorganic materials 0.000 description 86
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YXVFQADLFFNVDS-UHFFFAOYSA-N diammonium citrate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O YXVFQADLFFNVDS-UHFFFAOYSA-N 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 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
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
- C01B3/042—Decomposition of water
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a MoC/N-contemplated carbon/g-C 3 N 4 Composite photocatalyst, and preparation and application thereof. The invention provides MoC/N-contemplated carbon/g-C 3 N 4 The composite photocatalyst is prepared by uniformly loading MoC/N-supported carbon as a cocatalyst on a photocatalyst g-C 3 N 4 The invention provides application of MoC/N-supported carbon material as a cocatalyst of a photocatalyst, which can promote photo-generated electron transmission and separation, improve utilization efficiency of photo-generated charge and reduce g-C 3 N 4 Surface oxidation-reduction reaction energy barrier. MoC/N-dopped carbon/g-C prepared therefrom 3 N 4 The composite photocatalyst has high-efficiency photocatalytic water splitting hydrogen production activity, and solves the problems of high cost, less reserves of noble metal cocatalysts and incapability of large-scale application.
Description
Technical Field
The invention belongs to the technical field of nano photocatalyst materials. And more particularly to a MoC/nitrogen doped carbon/g-C 3 N 4 Composite photocatalyst, and preparation and application thereof.
Background
Solar energy is a clean renewable energy source, and the technology for preparing hydrogen by simulating solar photocatalytic decomposition of water is an economic and environment-friendly technology with development prospect. To date, a large number of semiconductor photocatalysts have been developed for photolytic hydrogen evolution, generally speaking, H at the photocatalyst surface 2 With O 2 The formation reaction of (a) is respectively assisted by reduction and oxidationCatalyst drive (nat. Rev. Mater.,2017,2, 17050). Wherein noble metal Pt with larger work function can easily form a Schottky barrier with a semiconductor, can be used as an excellent electron trapping trap, and promotes H due to good adsorption of protons 2 (chem. Rev.2020, 120,2, 919-985). However, the reverse reaction of water splitting also tends to occur on Pt nanoparticles, as Pt exhibits lower O 2 Overpotential for the reduction reaction (j.catalyst.2008, 259, 133-137). This problem can be avoided by using Ru (j.Phys.chem.c 2011, 115, 3057-3064) or Rh (angel.chem.int.ed.2006, 45, 7806-7809) instead of Pt to catalyze the water decomposition. In addition, the photocatalytic oxygen evolution half reaction is the determining step of the photocatalytic water decomposition rate, because it involves the reaction of H 2 O forms O 2 The four electron oxidation path of (2) requires an energy of 1.23 eV. To achieve a high rate of efficient water oxidation half reaction, noble metal oxides, e.g. RuO 2 (J.am.chem.Soc.2005, 127, 4150-4151) and IrO 2 (j.am.chem.soc.2009, 131, 926-927) and the like are considered to be the best oxygen evolution promoters, and commonly used photocatalysts are noble metal photocatalysts such as gold (Au), platinum (Pt) and the like, which have high photocatalytic activity, but are expensive and resource-shortage, so that the application of the noble metal photocatalysts is severely limited. Therefore, the development of novel non-noble metal promoters is the current focus of research.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the application of the non-noble metal material three-dimensional mesoporous carbon loaded molybdenum carbide (MoC/nitrogen doped carbon) in the cocatalyst serving as the photocatalyst, the cocatalyst can promote the transmission and separation of photo-generated electrons, improve the utilization efficiency of photo-generated charges, reduce the oxidation-reduction reaction energy barrier on the surface of the photocatalyst, and further load the photo-generated electrons on the photocatalyst g-C 3 N 4 The surface is obtained to be MoC/nitrogen doped with carbon/g-C 3 N 4 Composite photocatalyst material, compared to g-C 3 N 4 The photocatalyst shows higher efficient photocatalytic decomposition of the hydrogen production activity, is expected to realize solar energy conversion by an acceptable cost route, and has good application and developmentAnd (3) prospect.
The primary object of the present invention is to provide the use of MoC/nitrogen doped carbon as a cocatalyst for a photocatalyst.
It is another object of the present invention to provide the use of MoC/nitrogen doped carbon as a promoter in the preparation of photocatalysts.
Another object of the present invention is to provide a MoC/N-doped carbon/g-C 3 N 4 A composite photocatalyst.
It is a further object of the present invention to provide the MoC/nitrogen doped carbon/g-C 3 N 4 The application of the composite photocatalyst in the photocatalytic decomposition of water to produce hydrogen.
The invention discloses that three-dimensional mesoporous carbon loaded molybdenum carbide (MoC/nitrogen doped carbon) can be used as a cocatalyst of a photocatalyst so as to improve the photocatalytic hydrogen evolution rate of a main photocatalyst. Thus, the present invention first provides the use of a MoC/N-supported carbon as a cocatalyst for a photocatalyst.
Preferably, the photocatalyst is g-C 3 N 4 . The invention uniformly loads the MoC/nitrogen-doped carbon on the photocatalyst g-C 3 N 4 Surface, bulk photocatalyst g-C 3 N 4 Light is absorbed to generate photo-generated electrons and holes, and a promoter MoC/nitrogen doped carbon can promote photo-generated electron transmission and separation, so that the utilization efficiency of photo-generated charges is improved, and more importantly, the promoter can reduce g-C 3 N 4 Surface oxidation-reduction reaction energy barrier, and the obtained MoC/nitrogen doped carbon/g-C 3 N 4 The composite photocatalyst has high-efficiency photocatalytic water splitting hydrogen production activity.
The preparation method of the MoC/nitrogen doped carbon refers to a prior patent CN201811487558.1 of the inventor of the application.
As a preferred embodiment, the preparation method of the MoC/nitrogen doped carbon comprises the following steps:
6.05g of ammonium molybdate, 15.82g of diammonium citrate, 1.84g of hydrazine hydrochloride were dissolved in 70mL of deionized water, then a nanosilica sol (LUDOX AS-40colloidal silica,40wt% suspension in H) was added 2 O), stirring uniformly, and then using ammonia water to make the mixed solutionThe pH was adjusted to 6. Heating and stirring the mixed solution at 80 ℃ to form gel, further drying the water in the gel at 110 ℃, calcining the xerogel at 900 ℃ for 4 hours under the protection of nitrogen, etching and removing nano silicon dioxide by using hydrofluoric acid with the mass fraction of 2%, and carrying out suction filtration, washing, drying and grinding to obtain the MoC/nitrogen doped carbon cocatalyst.
MoC/nitrogen-doped carbon is obtained by loading MoC quantum dots on the surface of nitrogen-doped porous carbon, and can promote the transmission and separation of photogenerated electrons, improve the utilization efficiency of photogenerated charges, reduce the potential barrier of hydrogen evolution reaction and promote the progress of the hydrogen evolution reaction.
In addition, the invention also provides a method for doping carbon and g-C by MoC/nitrogen 3 N 4 The prepared MoC/nitrogen doped carbon/g-C 3 N 4 A composite photocatalyst.
As a preferred embodiment, the preparation method of the composite photocatalyst includes the steps of:
doping MoC/Nitrogen with carbon and g-C 3 N 4 Mixing, adding ethanol, grinding uniformly, and annealing under inert atmosphere to obtain the MoC/nitrogen doped carbon/g-C 3 N 4 A composite photocatalyst.
The invention is the MoC/nitrogen doped carbon/g-C 3 N 4 The preparation method of the composite photocatalyst uniformly loads MoC/nitrogen-doped carbon serving as a cocatalyst on g-C 3 N 4 The surface is obtained to be MoC/nitrogen doped with carbon/g-C 3 N 4 The composite photocatalyst material has the advantages of simple process, strong operability and good repeatability, can realize solar energy conversion by a low-cost route, and has good application prospect.
Preferably, the MoC/nitrogen doped carbon is mixed with g-C 3 N 4 The mass ratio of (2) is 1:5.67 to 19.
Preferably, the annealing treatment is carried out at a temperature of 150-300 ℃ for 1-6 hours.
Preferably, the ethanol is added in an amount corresponding to g-C 3 N 4 The mass ratio of (2) is 10-5: 1.
more preferably, the ethanolThe addition amount is equal to g-C 3 N 4 The mass ratio of (2) is 6.32-9.41: 1.
preferably, the milling is performed by ball milling or milling in an agate mortar.
Preferably, the inert atmosphere comprises a nitrogen atmosphere, an argon atmosphere.
The MoC/nitrogen doped carbon/g-C obtained by the invention 3 N 4 Shows high-efficiency photocatalytic decomposition of water to produce hydrogen activity, and is pure g-C 3 N 4 106.1 times of the photocatalyst, therefore, the application of the composite photocatalyst in the aspect of photocatalytic decomposition of water to produce hydrogen is also within the protection scope of the invention.
As a preferred embodiment, the g-C 3 N 4 The preparation method of (2) comprises the following steps: the urea is put in a ceramic crucible, covered with a cover, and reacted in a muffle furnace at 550 ℃ for 2 hours to obtain g-C 3 N 4 。
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a new application of novel non-noble metal MoC/nitrogen doped carbon as a cocatalyst of a photocatalyst, the MoC/nitrogen doped carbon material can promote the transmission and separation of photo-generated electrons, improve the utilization efficiency of the photo-generated electrons and reduce the g-C of the photocatalyst 3 N 4 The oxidation-reduction reaction energy barrier on the surface promotes the hydrogen evolution reaction, and effectively improves the g-C 3 N 4 Photocatalytic hydrogen evolution rate.
The MoC/nitrogen doped carbon cocatalyst has low cost, solves the problems of high cost, small reserves and incapability of large-scale application of noble metal cocatalysts, and has good application prospect.
Drawings
FIG. 1 is an XRD pattern of the co-catalyst MoC/nitrogen-doped carbon prepared in example 1
FIG. 2 is a TEM image of the co-catalyst MoC/nitrogen-doped carbon prepared in example 1
FIG. 3 shows the photocatalyst g-C prepared in example 2 3 N 4 Is of the XRD pattern of (C)
FIG. 4 shows a photocatalyst g-C prepared in example 2 3 N 4 TEM images of (a)
FIG. 5 shows MoC/N-doped carbon/g-C prepared in example 3 3 N 4 XRD pattern of the composite photocatalyst.
FIG. 6 is a MoC/N-doped carbon/g-C prepared in example 3 3 N 4 TEM image of composite photocatalyst
FIG. 7 is a MoC/N-doped carbon/g-C prepared in example 3 3 N 4 Composite photocatalyst, moC/nitrogen-doped carbon cocatalyst prepared in example 1, g-C prepared in example 2 3 N 4 The total hydrogen production amount of the photocatalyst and the composite photocatalysts prepared in comparative examples 1 to 4 accumulated with the irradiation time.
FIG. 8 shows MoC/N-doped carbon/g-C prepared in example 3 3 N 4 Composite photocatalyst and g-C prepared in example 2 3 N 4 Electrocatalytic hydrogen evolution polarization curve of photocatalyst.
FIG. 9 is a MoC/N-doped carbon/g-C prepared in example 3 3 N 4 Composite photocatalyst and g-C prepared in example 2 3 N 4 Photocurrent response curve of the photocatalyst.
Detailed Description
The invention is further described in connection with the accompanying drawings and the detailed description, which are not intended to be limiting in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
The instrument used for TEM analysis is JSM-2010 type projection electron microscope (TEM) of Japan electronic company to observe microscopic morphology of sample surface, acceleration voltage is 200KV, and the sample is prepared by dispersing absolute ethyl alcohol, then dripping copper mesh, and drying in air.
The apparatus used for XRD analysis was a physical Rigaku Ultima type IV X-ray diffractometer (XRD) characterization of the crystalline phase structure material of the final product prepared. The test conditions are Cu target, K alpha radiation, 40kV,40mA, step width of 0.02 DEG, and scanning range of 10-80 deg. And placing the powder in a groove of a sample table for flattening the powder, and directly detecting.
Nanosilica sol (LUDOX AS-40colloidal silica) was purchased from Sigma-Aldrich.
EXAMPLE 1 Co-catalyst MoC/Nitrogen doped carbon
1. Preparation
S1, 6.05g of ammonium molybdate, 15.82g of diammonium hydrogen citrate and 1.84g of hydrazine hydrochloride are dissolved in 70mL of deionized water, and then 20mL of nano silica sol (LUDOX AS-40colloidal silica,40wt) is added 2 O), stirring uniformly, and then adjusting the pH value of the mixed solution to 6 by ammonia water.
S2, heating and stirring the mixed solution at 80 ℃ to form gel, further drying the gel at 110 ℃ for 12 hours, and calcining the xerogel at 900 ℃ for 4 hours under the protection of nitrogen;
s3, adding the calcined product into a hydrofluoric acid solution with the mass fraction of 2 wt% (the hydrofluoric acid content is 30% higher than the amount required for theoretically removing silicon dioxide), etching and removing the nano silicon dioxide, and then carrying out suction filtration, washing with deionized water, drying at 80 ℃ for 10 hours, and grinding to obtain the MoC/nitrogen doped carbon cocatalyst.
2. Structural characterization
(1) FIG. 1 is an XRD pattern for the co-catalyst MoC/nitrogen doped carbon of this example showing four strong diffraction peaks at 36.8, 42.7, 62.1 and 74.7 corresponding to the (111), (200), (220) and (311) planes of MoC (PDF#: 65-0280), respectively. The characteristic peak at 2θ=26.2° corresponds to the (002) crystal plane of nitrogen-doped carbon, indicating successful synthesis of MoC/nitrogen-doped carbon composite material.
(2) Fig. 2 is a TEM image of the co-catalyst MoC/nitrogen doped carbon of this example, from which it can be seen that the MoC quantum dots have a particle size of less than 5nm and are uniformly supported on the nitrogen doped carbon surface.
EXAMPLE 2 photocatalyst g-C 3 N 4
1. Preparation
The urea is put in a ceramic crucible, covered with a cover, and reacted in a muffle furnace at 550 ℃ for 2 hours to obtain the photocatalyst g-C 3 N 4 。
2. Structural characterization
(1) FIG. 3 shows the embodiment g-C 3 N 4 Wherein two strong diffraction peaks are shown,located at 13.2℃and 27.5℃respectively corresponding to g-C 3 N 4 The (111) and (002) planes. Indicating that g-C is synthesized 3 N 4 Photocatalytic material.
(2) FIG. 4 shows the embodiment g-C 3 N 4 From the TEM image of (C), g-C can be seen 3 N 4 Is a two-dimensional nano-sheet.
EXAMPLE 3 MoC/Nitrogen doped carbon/g-C 3 N 4 Composite photocatalyst
1. Preparation
0.01g of the MoC/nitrogen-doped carbon prepared in example 1 and 0.19g of the g-C prepared in example 2 were reacted 3 N 4 Adding into agate mortar, adding 1.2g ethanol, grinding in agate mortar for 1 hr, and annealing at 200deg.C under nitrogen protection for 2 hr after ethanol volatilizes to obtain MoC/nitrogen doped carbon/g-C 3 N 4 A composite photocatalyst.
2. Characterization of
(1) FIG. 5 shows the MoC/N-doped carbon/g-C prepared in this example 3 N 4 XRD pattern of the composite photocatalyst. As can be seen from the XRD pattern, the characteristic peaks at 13.2℃and 27.5℃correspond to g-C 3 N 4 The (111) and (002) planes. The other two distinct characteristic peaks, located at 41.25℃and 47.95℃correspond to the (111) and (200) crystal planes of MoC (PDF#: 65-0280), respectively. Indicating that the MoC/nitrogen doped carbon/g-C is successfully prepared 3 N 4 A composite photocatalyst.
(2) FIG. 6 shows the MoC/N-doped carbon/g-C prepared in this example 3 N 4 TEM image of composite photocatalyst, from which it can be seen that promoter MoC/nitrogen-doped carbon is uniformly anchored in photocatalyst g-C 3 N 4 Is a surface of the substrate.
EXAMPLE 4 MoC/Nitrogen doped carbon/g-C 3 N 4 Composite photocatalyst
0.02g of the MoC/nitrogen-doped carbon prepared in example 1 and 0.18g of the g-C prepared in example 2 were reacted 3 N 4 Adding into agate mortar, adding 1.5g ethanol, grinding in agate mortar for 1 hr, volatilizing ethanol, annealing at 150deg.C under nitrogen protection for 6 hr to obtain MoC/nitrogen doped carbon/g-C 3 N 4 Composite photocatalysisAnd (3) an agent.
EXAMPLE 5 MoC/Nitrogen doped carbon/g-C 3 N 4 Composite photocatalyst
0.03g of the MoC/nitrogen-doped carbon prepared in example 1 and 0.17g of the g-C prepared in example 2 were reacted 3 N 4 Adding into agate mortar, adding 1.6g ethanol, grinding with agate mortar for 1 hr, and annealing at 300deg.C under nitrogen protection for 1 hr after ethanol is volatilized to obtain MoC/nitrogen doped carbon/g-C 3 N 4 A composite photocatalyst.
Comparative example 1
This comparative example provides a MoC/N-doped carbon/g-C 3 N 4 A composite photocatalyst was prepared as in example 3, except that the mass of MoC/nitrogen-doped carbon was 0.09g, g-C 3 N 4 The mass of the catalyst is 18g, and the mass of the ethanol is 150g, namely MoC/nitrogen doped carbon and g-C 3 N 4 The mass ratio of (2) is 0.5:99.5.
comparative example 2
This comparative example provides a MoC/N-doped carbon/g-C 3 N 4 The preparation method of the composite photocatalyst is the same as in example 3, except that the mass of MoC/nitrogen-doped carbon is 0.42g, namely MoC/nitrogen-doped carbon and g-C 3 N 4 The mass ratio of (2) is 70:30.
comparative example 3
This comparative example provides a MoC/N-doped carbon/g-C 3 N 4 The preparation method of the composite photocatalyst is the same as that of example 3, except that the annealing treatment is performed at 100 ℃ for 8 hours.
Comparative example 4
This comparative example provides a MoC/N-doped carbon/g-C 3 N 4 The preparation method of the composite photocatalyst is the same as that of example 3, except that the annealing treatment is performed at 400 ℃ for 1 hour.
Experimental example 1 photocatalytic water splitting hydrogen production experiment
1. Experimental method
MoC/Nitrogen-doped carbon/g-C prepared in example 3 3 N 4 Composite photocatalyst, moC/Nitrogen-doped carbon prepared in example 1, g-C prepared in example 2 3 N 4 The composite photocatalysts prepared in comparative examples 1 to 4 were subjected to a photocatalytic decomposition water production hydrogen test.
The photocatalytic water splitting reaction was performed in a labsorar 6A photocatalytic reaction system (beijing pofiril), and the entire system may be in communication with a vacuum pump. 20mg of the photocatalyst was added to a reactor containing 80mL of deionized water and 20mL of triethanolamine, and the mixture was subjected to ultrasonic dispersion for 3min, followed by stirring. The reactor was connected to the system and sealed, the whole system was evacuated to 2.0kPa with a vacuum pump, the reactor was kept at a constant temperature with 15 ℃ condensed water, and the suspension in the reactor was kept in suspension with magnetic stirring. The reactor is top-illuminated, a 300W xenon lamp is used as a light source, the input voltage is 220V, the current is 15A, and a light filter (A.M 1.5) can be assembled on a lamp cap. After the reaction starts, taking one sample every 30min through an automatic sample injection system, and sending the sample into an online gas chromatograph to detect H generated by the reaction 2 。
2. Experimental results
FIG. 7 is a MoC/N-doped carbon/g-C prepared in example 3 3 N 4 Composite photocatalyst, moC/Nitrogen-doped carbon prepared in example 1, g-C prepared in example 2 3 N 4 The total amount of hydrogen produced by the catalysis of the composite photocatalyst prepared in comparative examples 1-4 accumulated with the time of illumination.
As can be seen from FIG. 7, the total light is irradiated for 4 hours, g-C prepared in example 2 3 N 4 The total hydrogen production of the photocatalyst was 0.44. Mu. Mol. Under the same conditions, the MoC/nitrogen-doped carbon prepared in example 1 had no hydrogen production activity. Under the same conditions, the MoC/nitrogen-doped carbon/g-C prepared in example 3 3 N 4 The total hydrogen production of the composite photocatalyst was 46.68. Mu. Mol, therefore, moC/N-doped carbon/g-C 3 N 4 The hydrogen production rate of the composite photocatalyst is pure g-C 3 N 4 106.1 times of the photocatalyst. The result shows that the MoC/nitrogen doped carbon can effectively improve the g-C of the main photocatalyst 3 N 4 Is a photocatalytic hydrogen evolution rate. Therefore, the invention provides a high-efficiency composite photocatalyst MoC/nitrogen doped carbon/g-C 3 N 4 . Under the same conditions, the MoC/nitrogen blends prepared in comparative example 1, comparative example 2, comparative example 3 and comparative example 4heterocarbon/g-C 3 N 4 The total hydrogen production of the composite photocatalyst was 6.24, 10.56, 35.62, 27.43. Mu. Mol, respectively, which were less effective than example 3, indicating that the MoC/nitrogen-doped carbon/g-C prepared under the optimal control conditions 3 N 4 The composite photocatalyst has good photocatalytic activity.
Experimental example 2 electrocatalytic hydrogen evolution polarization curve
1. Experimental method
MoC/Nitrogen-doped carbon/g-C prepared in example 3 3 N 4 Composite photocatalyst, g-C prepared in example 2 3 N 4 The electrocatalytic hydrogen evolution polarization curves of the photocatalysts are compared.
Preparing a working electrode: mu.L of Nafion (5 wt%) solution was mixed with 5.0mg of MoC/nitrogen doped carbon/g-C 3 N 4 Composite photocatalyst or g-C 3 N 4 The photocatalyst was added to 1.0mL of ethanol and dispersed by ultrasound to give a suspension. 100. Mu.L of the suspension was applied dropwise to an FTO conductive glass substrate (2X 1 cm) 2 ) And (3) naturally drying, and annealing at 150 ℃ for 60min in an argon atmosphere to obtain the working electrode.
Photoelectrochemical testing was performed on an electrochemical workstation (CHI 650E) equipped with a three-electrode system, with platinum and Ag/AgCl (saturated KCl) electrodes as counter and reference electrodes, respectively. At 0.5M Na 2 SO 4 The solution was used as an electrolyte. At a scanning rate of 5 mV.s -1 The polarization curve of the electrocatalytic Hydrogen Evolution Reaction (HER) was tested.
2. Experimental results
FIG. 8 is a g-C prepared in example 2 3 N 4 Photocatalyst and MoC/Nitrogen-doped carbon/g-C prepared in example 3 3 N 4 Electrocatalytic hydrogen evolution polarization curve of the composite photocatalyst. Compared with pure g-C 3 N 4 MoC/Nitrogen doped carbon/g-C 3 N 4 The hydrogen evolution overpotential of (c) becomes smaller, which indicates that the promoter MoC/nitrogen-doped carbon can reduce the potential barrier of the hydrogen evolution reaction and promote the progress of the hydrogen evolution reaction.
Experimental example 3 photocurrent response curve
1. Experimental method
MoC/Nitrogen-doped carbon/g-C prepared in example 3 3 N 4 Composite photocatalyst, g-C prepared in example 2 3 N 4 The photocatalyst photocurrent response curves were compared.
Preparing a working electrode: mu.L of Nafion (5 wt%) solution was mixed with 5.0mg of MoC/nitrogen doped carbon/g-C 3 N 4 Composite photocatalyst or g-C 3 N 4 The photocatalyst was added to 1.0mL of ethanol and dispersed by ultrasound to give a suspension. 100. Mu.L of the suspension was applied dropwise to an FTO conductive glass substrate (2X 1 cm) 2 ) And (3) naturally drying, and annealing at 150 ℃ for 60min in an argon atmosphere to obtain the working electrode.
Photoelectrochemical testing was performed on an electrochemical workstation (CHI 650E) equipped with a three-electrode system, with platinum and Ag/AgCl (saturated KCl) electrodes as counter and reference electrodes, respectively. At 0.5M Na 2 SO 4 The solution was used as an electrolyte. A300W xenon lamp was used as a light source to record a transient photocurrent curve (i-t) at a voltage of 0.3V vs. Ag/AgCl.
2. Experimental results
FIG. 9 is a g-C prepared in example 2 3 N 4 Photocatalyst and MoC/Nitrogen-doped carbon/g-C prepared in example 3 3 N 4 Photocurrent response curve of the composite photocatalyst. MoC/Nitrogen doped carbon/g-C 3 N 4 Photocurrent density ratio g-C 3 N 4 The large size of the catalyst indicates that the catalyst promoter MoC/nitrogen doped carbon can accelerate charge transmission and improve the utilization efficiency of photo-generated electrons.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (8)
- MoC/Nitrogen doped carbonUse of a cocatalyst as a photocatalyst, characterized in that the photocatalyst is g-C 3 N 4 ；The preparation method of the MoC/nitrogen doped carbon comprises the following steps:6.05g of ammonium molybdate, 15.82g of diammonium hydrogen citrate and 1.84g of hydrazine hydrochloride are dissolved in 70mL of deionized water, then nano silica sol is added, the mixture is stirred uniformly, and then ammonia water is used for regulating the pH value of the mixed solution to 6; heating and stirring the mixed solution at 80 ℃ to form gel, further drying the water in the gel at 110 ℃, calcining the xerogel at 900 ℃ for 4 hours under the protection of nitrogen, etching and removing nano silicon dioxide by using hydrofluoric acid with the mass fraction of 2%, and carrying out suction filtration, washing, drying and grinding to obtain the MoC/nitrogen doped carbon cocatalyst.
- 2. MoC/nitrogen doped carbon/g-C 3 N 4 The composite photocatalyst is characterized in that the composite photocatalyst is prepared by doping carbon and g-C with MoC/nitrogen 3 N 4 Is prepared by the steps of;the preparation method of the MoC/nitrogen doped carbon comprises the following steps:6.05g of ammonium molybdate, 15.82g of diammonium hydrogen citrate and 1.84g of hydrazine hydrochloride are dissolved in 70mL of deionized water, then nano silica sol is added, the mixture is stirred uniformly, and then ammonia water is used for regulating the pH value of the mixed solution to 6; heating and stirring the mixed solution at 80 ℃ to form gel, further drying the water in the gel at 110 ℃, calcining the xerogel at 900 ℃ for 4 hours under the protection of nitrogen, etching and removing nano silicon dioxide by using hydrofluoric acid with the mass fraction of 2%, and carrying out suction filtration, washing, drying and grinding to obtain the MoC/nitrogen doped carbon cocatalyst.
- 3. The composite photocatalyst according to claim 2, wherein the preparation method of the composite photocatalyst comprises the steps of:doping MoC/Nitrogen with carbon and g-C 3 N 4 Mixing, adding ethanol, grinding uniformly, and annealing under inert atmosphere to obtain the MoC/nitrogen doped carbon/g-C 3 N 4 A composite photocatalyst.
- 4. The composite photocatalyst of claim 3, wherein the MoC/nitrogen doped carbon is mixed with g-C 3 N 4 The mass ratio of (2) is 1:5.67 to 19.
- 5. A composite photocatalyst according to claim 3, wherein the annealing treatment is carried out at a temperature of 150 to 300 ℃ for a time of 1 to 6 hours.
- 6. The composite photocatalyst according to claim 3, wherein the ethanol is added in an amount corresponding to g-C 3 N 4 The mass ratio of (2) is 5-10: 1.
- 7. a composite photocatalyst according to claim 3, wherein the milling is ball milling or milling in an agate mortar.
- 8. Use of the composite photocatalyst according to any one of claims 2 to 7 for photocatalytic decomposition of aqueous hydrogen.
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