WO2023245910A1 - Platinum single atom/cluster modified photosensitizing system, and preparation method therefor and use thereof - Google Patents
Platinum single atom/cluster modified photosensitizing system, and preparation method therefor and use thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003504 photosensitizing agent Substances 0.000 title abstract description 9
- 230000002165 photosensitisation Effects 0.000 title abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 25
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 16
- 239000011941 photocatalyst Substances 0.000 claims abstract description 13
- 208000017983 photosensitivity disease Diseases 0.000 claims abstract description 10
- 231100000434 photosensitization Toxicity 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 8
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 8
- 229940068041 phytic acid Drugs 0.000 claims description 8
- 239000000467 phytic acid Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000009920 chelation Effects 0.000 abstract description 2
- 230000005684 electric field Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000002256 photodeposition Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 11
- 238000011160 research Methods 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011206 ternary composite Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- IVHJCRXBQPGLOV-UHFFFAOYSA-N azanylidynetungsten Chemical compound [W]#N IVHJCRXBQPGLOV-UHFFFAOYSA-N 0.000 description 1
- FFBGYFUYJVKRNV-UHFFFAOYSA-N boranylidynephosphane Chemical compound P#B FFBGYFUYJVKRNV-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001948 isotopic labelling Methods 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
-
- B01J35/39—
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Definitions
- the invention relates to a near-infrared light photocatalyst for total water decomposition, and specifically refers to a platinum single atom/cluster modified photosensitization system and its preparation method and use.
- the in-situ light deposition method is used to selectively in-situ light-deposit platinum single atoms/clusters on carbon nitride in a nickel phytate/carbon nitride composite system, which can be used for near-infrared light (wavelength greater than 800 nm) photocatalysis. Completely decomposes water.
- WN tungsten nitride
- heterogeneous composite is to construct a near-infrared light-responsive cocatalyst by compounding a wide-bandgap catalyst that responds to ultraviolet or visible light to achieve complete water splitting under near-infrared light conditions. Due to the large control space and excellent performance of the catalyst system, this idea has become the current mainstream research idea.
- metal-organic complex photosensitizers have shown unique photophysical and chemical characteristics in the near-infrared region, and therefore have great potential in the field of water splitting (YJYuan, ZTYu, DQChen, ZGZou, Chem.Soc.Rev.2017,46,603- 631.).
- metal-organic complex photosensitizers it is theoretically feasible to use metal-organic complex photosensitizers to achieve complete water splitting performance under near-infrared light.
- current metal-organic complex photosensitizers still face the problem of poor photocharge separation under near-infrared light conditions.
- supporting noble metal single atom (NM-SA) cocatalysts can effectively promote the photocharge separation efficiency of photocatalysts, thereby improving the performance of total water splitting.
- NM-SA noble metal single atom
- noble metal single-atom cocatalysts are used to promote the photocharge separation efficiency of near-infrared-responsive metal-organic complex photosensitizers, it is possible to achieve near-infrared response.
- Infrared light ( ⁇ >800nm) complete water decomposition performance.
- the purpose of the present invention is to provide a new direction and idea to synthesize a photocatalyst that completely splits water with near-infrared light ( ⁇ >800nm).
- in-situ chelation or electrostatic adsorption is used to construct the nickel phytate (PA-Ni) complex on the surface of carbon nitride (PCN) to obtain the nickel phytate/carbon nitride composite system, and then under near-infrared light ( ⁇ >800nm), selectively illuminate and deposit platinum single atoms/clusters (Pt-SAC) in the nickel phytate/carbon nitride composite system through photosensitization to obtain a photocatalyst on the carbon nitride surface, and use it Complete water decomposition reaction under near-infrared light ( ⁇ >800nm).
- Pt-SAC platinum single atoms/clusters
- Step 1 Grind the urea evenly and put it into the crucible, then place it in a muffle furnace and calcine to obtain sample A.
- the mass of urea is 10.0g, the grinding time is 5min, the crucible capacity is 50.0mL, the heating rate is 2.3°C/min, the calcination temperature is 550°C, and the calcination time is 3h.
- Step 2 Measure the phytic acid solution and add absolute ethanol to the phytic acid solution to obtain a mixed solution B of phytic acid and ethanol.
- the concentration of the phytic acid solution is 70wt%, and the volume ratio of the phytic acid solution to absolute ethanol is 1:4.
- Step 3 Weigh nickel acetate tetrahydrate into a beaker, then add absolute ethanol and sample A. Next, ultrasonic is used to completely dissolve nickel acetate tetrahydrate, and then the prepared phytic acid/ethanol mixed solution B is added, stirred, centrifuged, washed with ethanol, and finally dried in an oven to obtain sample C, which is recorded as PA-Ni 1.1 @PCN .
- the ratio of the nickel acetate tetrahydrate, absolute ethanol, sample A and phytic acid/ethanol mixed solution B is 1.1mmol:50mL:200mg:25mL, the ultrasonic time is 15min, the stirring time is 6h, and the centrifugal speed is 7000r/min. , washed 5 times, oven temperature is 60°C.
- Step 4 Add ultrapure water to sample C, then ultrasonic until sample C is evenly dispersed, then add chloroplatinic acid solution, vacuum to remove the air in the solution, and illuminate and deposit for 5 hours under near-infrared light conditions of ⁇ >800nm to obtain The sample obtained after the catalyst was centrifuged, washed with ethanol, and dried was recorded as PA-Ni 1.1 @PCN/Pt 5hNIR .
- the ratio of sample C, ultrapure water and chloroplatinic acid solution is 1g:50mL:2.68mL.
- the concentration of chloroplatinic acid solution is 1.15 ⁇ 10 -2 M.
- the centrifugal speed is 7000r/min. Wash with ethanol 5 times. Drying temperature is 60°C.
- the advantage of the present invention is that it can obtain platinum single atoms/clusters without the need for additional high temperatures, additional electric fields, and expensive and complex equipment, and the obtained catalytic active sites are not randomly distributed, but are consistent with the catalytic reaction process. corresponding.
- platinum single atoms/clusters were loaded into a photosensitized system using low-energy near-infrared light.
- Figure 1 is the extended X-ray absorption fine structure spectrum of the sample in the embodiment of the present invention. It can be seen from the figure that there are two main peaks in R space, namely 2.04 and They are attributed to Pt-N coordination and Pt-Pt bonds (formation of platinum clusters) respectively.
- FIG. 2 is the ultraviolet-visible diffuse reflection absorption spectrum (UV-Vis) of the sample prepared in the embodiment of the present invention. It can be seen from the figure that the PA-Ni 1.1 @PCN/Pt 5hNIR ternary composite system exhibits good near-infrared light Absorption ( ⁇ >800nm).
- Figure 3 is a near-infrared total water splitting performance diagram of the PA-Ni 1.1 @PCN/Pt 5hNIR ternary composite system in the embodiment of the present invention. It can be seen from the figure that the system shows good complete water splitting performance under near-infrared light with a wavelength greater than 800nm.
- the amounts of hydrogen and oxygen produced after 24 hours are 1.4 ⁇ mol and 0.65 ⁇ mol respectively, which are very close to Theoretically, the molar ratio of hydrogen and oxygen produced by water decomposition.
- the photocatalytic activity did not decay after continuous irradiation for 48 hours, indicating that the catalyst has good stability.
- Figure 4 shows the 18 O- of the PA-Ni 1.1 @PCN/Pt 5hNIR ternary composite system after being irradiated with near-infrared light ( ⁇ >800nm) for 48 hours in isotope water (H 2 18 O, 98%) in the embodiment of the present invention. Isotope labeling map. From the figure, we can see 18 O 2 as the main ground signal, which means that O 2 originates from water decomposition.
- Step 1 Grind 10.0g of urea for 5 minutes, put it evenly into a 50.0mL crucible, and then place it in a muffle furnace to calcine at 550°C, 2.3°C/min for 3 hours to obtain sample A.
- Step 2 Measure 5.0 mL of phytic acid solution (70wt%) and add 20 mL of absolute ethanol to obtain phytic acid/ethanol mixed solution B.
- Step 3 Weigh 1.1 mmol of nickel acetate tetrahydrate into a beaker, then add 50 mL of absolute ethanol and 200 mg of sample A. Next, ultrasonic for 15 minutes until nickel acetate tetrahydrate is completely dissolved, and then add 25 mL of the prepared phytic acid/ethanol mixed solution B. Stir thoroughly for 6h. Then centrifuge at 7000r/min, wash with ethanol 5 times, and finally dry in an oven at 60°C to obtain sample C, which is recorded as PA-Ni 1.1 @PCN.
- Step 4 Add sample C to 50 mL of ultrapure water, then sonicate for 5 minutes until sample C is evenly dispersed, then add 2.68 mL of chloroplatinic acid solution with a concentration of 1.15 ⁇ 10 -2 M, and vacuum several times to remove the air in the solution , the catalyst obtained after illumination deposition for 5 hours under the condition of near-infrared light ( ⁇ >800nm) was centrifuged at 7000r/min, washed with ethanol 5 times, and dried in an oven at 60°C. The obtained sample was recorded as PA-Ni 1.1 @PCN/ Pt 5hNIR .
- Platinum single atoms/clusters promote the separation of photogenerated charges in the PA-Ni/PCN photosensitization system, thereby achieving full photocatalytic water splitting performance at wavelengths greater than 800 nanometers, and the photocatalytic activity is maintained under continuous irradiation for 48 hours. No attenuation and very good stability.
Abstract
The present invention relates to a photocatalyst for overall water splitting under near-infrared light, in particular to a platinum single atom/cluster modified photosensitizing system, and a preparation method therefor and the use thereof. The preparation method comprises: first constructing a nickel phytate complex on the surface of carbon nitride by means of in-situ chelation or electrostatic adsorption to obtain a nickel phytate/carbon nitride composite system; and then, under the conditions of near-infrared light, subjecting platinum single atoms/clusters to selective photodeposition on the surface of carbon nitride in the nickel phytate/carbon nitride composite system by means of photosensitization to obtain a photocatalyst, and using same in an overall water splitting reaction under near-infrared light. The present invention has the following advantages: platinum single atoms/clusters can be obtained without additional high temperature, additional electric field and expensive and complex equipment; the obtained catalytic active sites are in one-to-one correspondence to the catalytic reaction process instead of being randomly distributed; and the loading of the platinum single atoms/clusters into a photosensitizing system is achieved by means of low-energy-consumption near-infrared light for the first time.
Description
本发明涉及近红外光全分解水光催化剂，特指一种铂单原子/簇修饰的光敏化体系及制备方法和用途。利用原位光照沉积的方法在植酸镍/氮化碳复合体系中选择性地将铂单原子/簇原位光沉积在氮化碳上，可用于近红外光(波长大于800nm以上)光催化全分解水。The invention relates to a near-infrared light photocatalyst for total water decomposition, and specifically refers to a platinum single atom/cluster modified photosensitization system and its preparation method and use. The in-situ light deposition method is used to selectively in-situ light-deposit platinum single atoms/clusters on carbon nitride in a nickel phytate/carbon nitride composite system, which can be used for near-infrared light (wavelength greater than 800 nm) photocatalysis. Completely decomposes water.
近年来，在能源枯竭问题日趋紧张以及环境问题日趋严峻的大背景下，利用光催化全分解水制取氢气作为绿色燃料被认为是未来可再生能源技术应用的基础(D.M.Zhao,Y.Q.Wang,C.L.Dong,Y.C.Huang,J.Chen,F.Xue,S.H.Shen,L.J.Guo,Nat.Energy 2021,6,388-397)。在实际应用中，充分利用太阳光以获得较高的效率仍然是一个巨大的挑战。根据太阳光响应的范围，目前已开发的能全分解水的材料基本上都是紫外光或者可见光响应的半导体材料，绝大部分光催化剂不能在近红外光条件下进行全分解水反应。从太阳光谱组成来看，近红外光区达50％以上(Z.C.Lian,M.Sakamoto,J.Vequizo,C.Ranasinghe,A.Yamakata,T.Nagai,K.Kimoto,Y.Kobayashi,N.Tamai,T.Teranishi,J.Am.Chem.Soc.2019,141,2446-2450.)。因此，为最大限度利用太阳能，开发近红外光响应的光催化全分解水光催化剂成为当前化学反应工程领域研究的热点。In recent years, under the background of increasingly tense energy depletion issues and increasingly severe environmental problems, the use of photocatalytic complete water splitting to produce hydrogen as a green fuel is considered to be the basis for the application of future renewable energy technologies (D.M. Zhao, Y.Q. Wang, C.L. Dong, Y.C. Huang, J. Chen, F. Xue, S. H. Shen, L. J. Guo, Nat. Energy 2021, 6, 388-397). In practical applications, fully utilizing sunlight to achieve high efficiency remains a huge challenge. According to the range of solar light response, currently developed materials that can fully decompose water are basically semiconductor materials that respond to ultraviolet or visible light. Most photocatalysts cannot fully decompose water under near-infrared light conditions. Judging from the composition of the solar spectrum, the near-infrared light region reaches more than 50% (Z.C.Lian, M.Sakamoto, J.Vequizo, C.Ranasinghe, A.Yamakata, T.Nagai, K.Kimoto, Y.Kobayashi, N.Tamai , T. Teranishi, J. Am. Chem. Soc. 2019, 141, 2446-2450.). Therefore, in order to maximize the utilization of solar energy, the development of near-infrared light-responsive photocatalysts for total water splitting has become a current research focus in the field of chemical reaction engineering.
近年来，国内外学者们围绕着近红外光全分解水光催化剂开展了系列研究工作，取得了一些突破性研究进展。所报道的催化剂设计思路基本可以分为能带调控和异质复合两类。能带调控思路通过能带结构的设计和调控，直接构建近红外光响应的窄带隙半导体催化剂。2017年华东理工大学杨化桂教授等人报道的氮化钨(WN)光催化剂带隙为1.55eV，可以实现近红外光(λ＝765nm)全分解水性能(Y.L.Wang,T.Nie,Y.H.Li,X.L.Wang,L.R.Zheng,A.P.Chen,X.Q.Gong,H.G.Yang,Angew.Chem.Int.Ed.2017,129,7538-7542.)。但由于自身带隙中存在杂质能级，往往使得该类窄带隙半导体催化剂催化活性表现较不理想，稳定性也较差(Y.H.Sang,Z.H.Zhao,M.W.Zhao,P.Hao,Y.H.Leng,H.Liu,Adv.Mater.2015,27,363-369.)。异质复合思路主要是通过在紫外或可见光响应的宽带隙催化剂上复合构建近红外光响应的助催化剂，实现近红外光条件下的全分解水。 由于催化剂体系的调控空间较大、性能优异，这种思路已成为当前主流的研究思路。2020年中国科学院兰州化学物理研究所吕功煊教授等人率先利用NaYF
4–Yb
3+/Er
3+稀土元素上转换效应与半导体CdS和rGO复合实现了特定波长在980nm的近红外光全分解水性能(W.Gao,Y.Q.Wu,G.X.Lu,Catal.Sci.Technol.2020,10,2389-2397.)。与稀土元素上转换光催化体系相比，窄带隙半导体复合光催化体系不仅价格更为低廉，而且能够吸收更宽范围的近红外光，最近也更为受到关注。所以之后，2021年吕功煊教授等人首次利用窄带隙半导体磷化硼(BP)与C
3N
4复合实现了λ＝730nm近红外条件下的全分解水性能(B.Tian,Y.Q.Wu,G.X.Lu,Appl.Catal.B-Environ.2021,280,119410.)。此外，2021年上海电力大学李和兴教授等人构建W
2N窄带隙半导体与C和TiO
2一起复合的光催化体系实现了波长大于700nm的近红外光全分解水性能(S.Q.Gong,J.C.Fan,V.Cecen,C.P.Huang,Y.L.Min,Q.J.Xu,H.X.Li,Chem.Eng.J.2021,405,126913.)。2020年苏州大学康振辉教授等人将WO
2半导体(带隙为0.6eV)与碳量子点和Na
xWO
3复合，首次实现了波长大于760nm的近红外光全分解水性能(J.Zhao,C.A.Liu,H.B.Wang,Y.J.Fu,C.Zhu,H.Huang,F.Liao,Y.Liu,M.W.Shao,Z.H.Kang,Catal.Today 2020,340,152-160.)。尽管上述工作已经极大地推动了该研究领域迅速发展，但在长波长(特别是800nm以上)近红外光响应全分解水光催化剂体系上仍存在活性低、稳定性差等问题。因此，开发800nm以上近红外光响应的高效稳定全分解水光催化剂体系仍然是一个巨大挑战。
In recent years, domestic and foreign scholars have carried out a series of research work on near-infrared light photocatalysts for total water splitting and achieved some breakthrough research progress. The reported catalyst design ideas can basically be divided into two categories: energy band regulation and heterogeneous composite. The idea of energy band regulation directly constructs a narrow bandgap semiconductor catalyst that responds to near-infrared light through the design and regulation of the energy band structure. In 2017, Professor Yang Huagui of East China University of Science and Technology and others reported that the tungsten nitride (WN) photocatalyst has a band gap of 1.55eV and can achieve full water splitting performance with near-infrared light (λ = 765nm) (YLWang, T.Nie, YHLi, XLWang, LRZheng,APChen,XQGong,HGYang,Angew.Chem.Int.Ed.2017,129,7538-7542.). However, due to the existence of impurity energy levels in its own band gap, the catalytic activity of this type of narrow band gap semiconductor catalysts is often less than ideal and the stability is also poor (YHSang, ZHZhao, MWZhao, P.Hao, YHLeng, H.Liu, Adv. Mater.2015,27,363-369.). The main idea of heterogeneous composite is to construct a near-infrared light-responsive cocatalyst by compounding a wide-bandgap catalyst that responds to ultraviolet or visible light to achieve complete water splitting under near-infrared light conditions. Due to the large control space and excellent performance of the catalyst system, this idea has become the current mainstream research idea. In 2020, Professor Lv Gongxuan from the Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, and others took the lead in using the NaYF 4 –Yb 3+ /Er 3+ rare earth element upconversion effect to combine with semiconductor CdS and rGO to achieve complete water splitting performance with near-infrared light at a specific wavelength of 980nm. (W. Gao, YQ Wu, GX Lu, Catal. Sci. Technol. 2020, 10, 2389-2397.). Compared with rare earth element upconversion photocatalytic systems, narrow-bandgap semiconductor composite photocatalytic systems are not only cheaper, but also capable of absorbing a wider range of near-infrared light, and have recently attracted more attention. Therefore, in 2021, Professor Lu Gongxuan and others used the narrow band gap semiconductor boron phosphide (BP) and C 3 N 4 to achieve full water splitting performance under λ = 730nm near-infrared conditions for the first time (B.Tian, YQWu, GXLu, Appl .Catal.B-Environ.2021,280,119410.). In addition, in 2021, Professor Li Hexing of Shanghai Electric Power University and others constructed a photocatalytic system in which W 2 N narrow band gap semiconductor was combined with C and TiO 2 to achieve full water splitting performance with near-infrared light with a wavelength greater than 700 nm (SQGong, JCFan, V.Cecen ,CPHuang,YLMin,QJXu,HXLi,Chem.Eng.J.2021,405,126913.). In 2020, Professor Kang Zhenhui of Suzhou University and others combined WO 2 semiconductor (band gap 0.6 eV ) with carbon quantum dots and Na ,HBWang,YJFu,C.Zhu,H.Huang,F.Liao,Y.Liu,MWShao,ZHKang,Catal.Today 2020,340,152-160.). Although the above work has greatly promoted the rapid development of this research field, there are still problems such as low activity and poor stability in long-wavelength (especially above 800nm) near-infrared light-responsive total water splitting photocatalyst systems. Therefore, it is still a huge challenge to develop an efficient and stable photocatalyst system for total water splitting with near-infrared light response above 800 nm.
对于半导体要实现波长大于800nm的全分解水性能是非常具有挑战性的工作，不仅需要理论带隙窄于1.55eV，而且导价带必须横跨水分解的氧化还原电位(1.23eV)，这几乎到达了半导体改性的极限。因此，需要寻找其他在近红外区具有光电响应的材料来替代这类窄带隙半导体。近年来，金属有机配合物光敏化剂在近红外区表现出独特的光物理和化学特征，因此在水分解领域颇具潜力(Y.J.Yuan,Z.T.Yu,D.Q.Chen,Z.G.Zou,Chem.Soc.Rev.2017,46,603-631.)。比如：2015年中国科学院长春光学精密机械与物理研究所孔祥贵教授等人首次结合有机铂光敏化剂在过硫酸盐作牺牲剂的情况实现了λ＝980nm水分解产氧半反应(X.M.Liu,H.C.Chen,X.G.Kong,Y.L.Zhang,L.P.Tu,Y.L.Chang,F.Wu,T.T.Wang,J.N.H.Reek,A.M.Brouwer,H.Zhang,Chem.Commun.2015,51, 13008-13011.)。2014年，北京大学李兴国教授课题组利用有机锌配体与石墨相氮化碳结合构建的光催化体系，首次在乳酸作牺牲剂的条件下实现了在近红外光下(λ＝700nm)的水分解产氢性能(X.H.Zhang,L.J.Yu,C.S.Zhuang,T.Y.Peng,R.J.Li,X.G.Li,ACS Catal.2014,4,162.)。最近，我们课题组利用有机镍配体(植酸镍)与石墨相氮化碳结合构建的光催化体系，首次在甲醇作牺牲剂的条件下实现了波长大于900nm的光催化水分解产氢性能(Y.Y.Huang,Y.P.Jian,L.H.Li,D.Li,Z.Y.Fang,W.X.Dong,Y.H.Lu,B.F.Luo,R.J.Chen,Y.C.Yang,M.Chen,W.D.Shi,Angew.Chem.Int.Ed.2021,60,5245-5249.)。受到之前这些工作的启发，利用金属有机配合物光敏化剂去实现近红外光下的全分解水性能理论上是可行的。然而目前金属有机配合物光敏化剂还面临着在近红外光条件下光电荷分离效果差的问题。最近，负载贵金属单原子(noble metal single atom:NM-SA)助催化剂可以有效促进光催化剂的光电荷分离效率，从而提高全分解水的性能。比如：武汉大学化学与分子科学学院彭天右教授等人通过级联电荷转移和Pt单原子催化位点，将卟啉共轭聚合物接枝到BiVO
4上，用于高效的Z-Scheme全水分解(J.M.Wang,L.Xu,T.X.Wang,R.J.Li,Y.X.Zhang,J.Zhang,T.Y.Peng,Adv.Energy Mater.2021,11,2003575.)。陕西科技大学环境科学与工程学院王传义教授等人在CdS纳米催化剂上负载了Pd单原子助催化剂从而实现了高效地全分解水性能(W.Li,X.S.Chu,F.Wang,Y.Y.Dang,X.Y.Liu,T.H.Ma,J.Y.Li,C.Y.Wang,Appl.Catal.B-Environ.2022,304,121000)。考虑到金属有机配合物光敏化剂和贵金属单原子的特点和优势，如果使用贵金属单原子助催化剂来促进近红外响应的金属有机配合物光敏化剂的光电荷分离效率，就有可能能够实现近红外光(λ>800nm)全分解水的性能。
It is very challenging for semiconductors to achieve full water splitting performance at wavelengths greater than 800nm. Not only does the theoretical band gap need to be narrower than 1.55eV, but the valence band must span the redox potential of water splitting (1.23eV), which is almost The limit of semiconductor modification has been reached. Therefore, there is a need to find other materials with photoelectric response in the near-infrared region to replace such narrow bandgap semiconductors. In recent years, metal-organic complex photosensitizers have shown unique photophysical and chemical characteristics in the near-infrared region, and therefore have great potential in the field of water splitting (YJYuan, ZTYu, DQChen, ZGZou, Chem.Soc.Rev.2017,46,603- 631.). For example: In 2015, Professor Kong Xianggui and others from the Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, for the first time combined an organic platinum photosensitizer with persulfate as a sacrificial agent to achieve λ = 980nm water splitting to produce oxygen half-reaction (XMLiu, HCChen, XGKong,YLZhang,LPTu,YLChang,F.Wu,TTWang,JNHReek,AMBrouwer,H.Zhang,Chem.Commun.2015,51, 13008-13011.). In 2014, the research group of Professor Li Xingguo of Peking University used a photocatalytic system constructed by combining organic zinc ligands with graphite phase carbon nitride, and for the first time achieved water catalysis under near-infrared light (λ = 700nm) using lactic acid as a sacrificial agent. Decomposition hydrogen production performance (XHZhang, LJYu, CSZhuang, TYPeng, RJLi, XGLi, ACS Catal. 2014, 4, 162.). Recently, our research group used a photocatalytic system constructed by combining an organic nickel ligand (nickel phytate) with graphite phase carbon nitride, and for the first time achieved photocatalytic water splitting and hydrogen production performance with a wavelength greater than 900 nm using methanol as a sacrificial agent. (YYHuang,YPJian,LHLi,D.Li,ZYFang,WXDong,YHLu,BFLuo,RJChen,YCYang,M.Chen,WDShi,Angew.Chem.Int.Ed.2021,60,5245-5249.). Inspired by these previous works, it is theoretically feasible to use metal-organic complex photosensitizers to achieve complete water splitting performance under near-infrared light. However, current metal-organic complex photosensitizers still face the problem of poor photocharge separation under near-infrared light conditions. Recently, supporting noble metal single atom (NM-SA) cocatalysts can effectively promote the photocharge separation efficiency of photocatalysts, thereby improving the performance of total water splitting. For example: Professor Peng Tianyou and others from the School of Chemistry and Molecular Science of Wuhan University grafted porphyrin conjugated polymers onto BiVO 4 through cascade charge transfer and Pt single-atom catalytic sites for efficient Z-Scheme synthesis. Water decomposition (JMWang, L. Xu, TX Wang, RJ Li, YX Zhang, J. Zhang, TY Peng, Adv. Energy Mater. 2021, 11, 2003575.). Professor Wang Chuanyi and others from the School of Environmental Science and Engineering of Shaanxi University of Science and Technology loaded Pd single-atom cocatalysts on CdS nanocatalysts to achieve efficient and complete water splitting performance (W.Li,XSchu,F.Wang,YYDang,XYLiu,THMa, JYLi, CYWang, Appl. Catal. B-Environ. 2022, 304, 121000). Considering the characteristics and advantages of metal-organic complex photosensitizers and noble metal single atoms, if noble metal single-atom cocatalysts are used to promote the photocharge separation efficiency of near-infrared-responsive metal-organic complex photosensitizers, it is possible to achieve near-infrared response. Infrared light (λ>800nm) complete water decomposition performance.
发明内容Contents of the invention
本发明的目的在于提供一个新的方向和思路去合成近红外光(λ>800nm)全分解水的光催化剂。首先采用原位螯合作用或静电吸附手段实现植酸镍(PA-Ni)配合物在氮化碳(PCN)表面的构筑得到植酸镍/氮化碳复合体系，然后在近红外光(λ>800nm)的条件下通过光敏化作用在植酸镍/氮化碳复合体系中选择性地光照沉积铂单原子/簇(Pt-SAC)在氮化碳表面上得到光催化剂，并将其用于近红外光(λ>800nm)全分解水反应。The purpose of the present invention is to provide a new direction and idea to synthesize a photocatalyst that completely splits water with near-infrared light (λ>800nm). First, in-situ chelation or electrostatic adsorption is used to construct the nickel phytate (PA-Ni) complex on the surface of carbon nitride (PCN) to obtain the nickel phytate/carbon nitride composite system, and then under near-infrared light (λ >800nm), selectively illuminate and deposit platinum single atoms/clusters (Pt-SAC) in the nickel phytate/carbon nitride composite system through photosensitization to obtain a photocatalyst on the carbon nitride surface, and use it Complete water decomposition reaction under near-infrared light (λ>800nm).
本发明具体的技术方案，包括以下几个步骤：The specific technical solution of the present invention includes the following steps:
步骤1：尿素研磨均匀放入坩埚内，然后置于马弗炉中煅烧得到样品A。Step 1: Grind the urea evenly and put it into the crucible, then place it in a muffle furnace and calcine to obtain sample A.
所述的尿素质量为10.0g，研磨时间为5min，坩埚容量为50.0mL，升温速率为2.3℃/min，煅烧温度为550℃，煅烧时间为3h。The mass of urea is 10.0g, the grinding time is 5min, the crucible capacity is 50.0mL, the heating rate is 2.3°C/min, the calcination temperature is 550°C, and the calcination time is 3h.
步骤2：量取植酸溶液，向植酸溶液中加入无水乙醇，得到植酸和乙醇的混合溶液B。Step 2: Measure the phytic acid solution and add absolute ethanol to the phytic acid solution to obtain a mixed solution B of phytic acid and ethanol.
所述的植酸溶液的浓度为70wt％，植酸溶液与无水乙醇的体积比为1:4。The concentration of the phytic acid solution is 70wt%, and the volume ratio of the phytic acid solution to absolute ethanol is 1:4.
步骤3：称取四水醋酸镍置于烧杯中，然后加入无水乙醇和样品A。接下来超声使得四水醋酸镍完全溶解，然后加入已配置好的植酸/乙醇的混合溶液B，搅拌、离心，乙醇洗涤，最后烘箱中烘干，得到样品C记为PA-Ni
1.1@PCN。
Step 3: Weigh nickel acetate tetrahydrate into a beaker, then add absolute ethanol and sample A. Next, ultrasonic is used to completely dissolve nickel acetate tetrahydrate, and then the prepared phytic acid/ethanol mixed solution B is added, stirred, centrifuged, washed with ethanol, and finally dried in an oven to obtain sample C, which is recorded as PA-Ni 1.1 @PCN .
所述四水醋酸镍、无水乙醇、样品A和植酸/乙醇的混合溶液B的比例为1.1mmol：50mL：200mg：25mL，超声时间为15min，搅拌时间为6h，离心转数7000r/min，洗涤5遍，烘箱温度为60℃。The ratio of the nickel acetate tetrahydrate, absolute ethanol, sample A and phytic acid/ethanol mixed solution B is 1.1mmol:50mL:200mg:25mL, the ultrasonic time is 15min, the stirring time is 6h, and the centrifugal speed is 7000r/min. , washed 5 times, oven temperature is 60℃.
步骤4：向样品C加入超纯水，然后超声待样品C分散均匀，接着加入氯铂酸溶液，并抽真空排除溶液中的空气，在λ>800nm的近红外光条件下光照沉积5h，得到的催化剂经离心、乙醇洗涤、干燥后得到的样品记为PA-Ni
1.1@PCN/Pt
5hNIR。
Step 4: Add ultrapure water to sample C, then ultrasonic until sample C is evenly dispersed, then add chloroplatinic acid solution, vacuum to remove the air in the solution, and illuminate and deposit for 5 hours under near-infrared light conditions of λ>800nm to obtain The sample obtained after the catalyst was centrifuged, washed with ethanol, and dried was recorded as PA-Ni 1.1 @PCN/Pt 5hNIR .
样品C、超纯水和氯铂酸溶液的比例为1g：50mL：2.68mL，氯铂酸溶液的浓度为1.15×10
-2M，离心转数为7000r/min，乙醇洗涤5遍，干燥温度为60℃。
The ratio of sample C, ultrapure water and chloroplatinic acid solution is 1g:50mL:2.68mL. The concentration of chloroplatinic acid solution is 1.15×10 -2 M. The centrifugal speed is 7000r/min. Wash with ethanol 5 times. Drying temperature is 60℃.
本发明的优点在于不需要额外高温和额外电场以及不需要昂贵复杂的设备即可获得铂单原子/簇，而且所得到的催化活性位点不是随意分布的，而是与催化反应过程一一相对应的。首次通过低能耗的近红外光实现了铂单原子/簇在光敏化体系中的负载。The advantage of the present invention is that it can obtain platinum single atoms/clusters without the need for additional high temperatures, additional electric fields, and expensive and complex equipment, and the obtained catalytic active sites are not randomly distributed, but are consistent with the catalytic reaction process. corresponding. For the first time, platinum single atoms/clusters were loaded into a photosensitized system using low-energy near-infrared light.
图1为本发明实施例中样品的扩展X射线吸收精细结构谱，从图中可以看到在R空间中展示出两个主要的峰，分别是2.04和
其分别归因于Pt-N配位和Pt-Pt键(形成了铂簇)。
Figure 1 is the extended X-ray absorption fine structure spectrum of the sample in the embodiment of the present invention. It can be seen from the figure that there are two main peaks in R space, namely 2.04 and They are attributed to Pt-N coordination and Pt-Pt bonds (formation of platinum clusters) respectively.
图2为本发明实施例中所制备样品的紫外可见漫反射吸收光谱(UV-Vis)，从图上可以看到PA-Ni
1.1@PCN/Pt
5hNIR三元复合体系表现出良好的近红外光吸收 (λ>800nm)。
Figure 2 is the ultraviolet-visible diffuse reflection absorption spectrum (UV-Vis) of the sample prepared in the embodiment of the present invention. It can be seen from the figure that the PA-Ni 1.1 @PCN/Pt 5hNIR ternary composite system exhibits good near-infrared light Absorption (λ>800nm).
图3为本发明实施例中PA-Ni
1.1@PCN/Pt
5hNIR三元复合体系的近红外全分解水性能图。从图中可以看到该体系在波长大于800nm的近红外光下表现出良好的全分解水性能，其中在24h后所产生的的氢气和氧气的量分别是1.4μmol和0.65μmol，其非常接近理论上水分解产氢产氧的摩尔比。持续照射48h光催化活性并没有衰减，表明催化剂具有很好的稳定性。
Figure 3 is a near-infrared total water splitting performance diagram of the PA-Ni 1.1 @PCN/Pt 5hNIR ternary composite system in the embodiment of the present invention. It can be seen from the figure that the system shows good complete water splitting performance under near-infrared light with a wavelength greater than 800nm. The amounts of hydrogen and oxygen produced after 24 hours are 1.4 μmol and 0.65 μmol respectively, which are very close to Theoretically, the molar ratio of hydrogen and oxygen produced by water decomposition. The photocatalytic activity did not decay after continuous irradiation for 48 hours, indicating that the catalyst has good stability.
图4为本发明实施例中PA-Ni
1.1@PCN/Pt
5hNIR三元复合体系在同位素水(H
2
18O，98％)中使用近红外光(λ>800nm)照射48h后的
18O-同位素标记图。从图中可以看到
18O
2作为主要地信号，这意味着O
2来源于水分解。
Figure 4 shows the 18 O- of the PA-Ni 1.1 @PCN/Pt 5hNIR ternary composite system after being irradiated with near-infrared light (λ>800nm) for 48 hours in isotope water (H 2 18 O, 98%) in the embodiment of the present invention. Isotope labeling map. From the figure, we can see 18 O 2 as the main ground signal, which means that O 2 originates from water decomposition.
下面结合实施例对本发明进行详细说明，以使本领域技术人员更好地理解本发明，但本发明并不局限于以下实施例。The present invention will be described in detail below in conjunction with the examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
实施例1Example 1
步骤1：10.0g尿素研磨5min后均匀放入50.0mL坩埚内，然后置于马弗炉以550℃，2.3℃/min，煅烧3h，得到样品A。Step 1: Grind 10.0g of urea for 5 minutes, put it evenly into a 50.0mL crucible, and then place it in a muffle furnace to calcine at 550°C, 2.3°C/min for 3 hours to obtain sample A.
步骤2：量取5.0mL的植酸溶液(70wt％)加入20mL的无水乙醇，得到植酸/乙醇混合溶液B。Step 2: Measure 5.0 mL of phytic acid solution (70wt%) and add 20 mL of absolute ethanol to obtain phytic acid/ethanol mixed solution B.
步骤3：称取1.1mmol的四水醋酸镍置于烧杯中，然后加入50mL的无水乙醇和200mg的样品A。接下来超声15min待四水醋酸镍完全溶解，然后加入25mL已配置好的植酸/乙醇混合溶液B。充分搅拌6h。然后7000r/min进行离心，并用乙醇洗涤5遍，最后在60℃烘箱中烘干，得到样品C记为PA-Ni
1.1@PCN。
Step 3: Weigh 1.1 mmol of nickel acetate tetrahydrate into a beaker, then add 50 mL of absolute ethanol and 200 mg of sample A. Next, ultrasonic for 15 minutes until nickel acetate tetrahydrate is completely dissolved, and then add 25 mL of the prepared phytic acid/ethanol mixed solution B. Stir thoroughly for 6h. Then centrifuge at 7000r/min, wash with ethanol 5 times, and finally dry in an oven at 60°C to obtain sample C, which is recorded as PA-Ni 1.1 @PCN.
步骤4：将样品C加入50mL的超纯水，然后超声5min待样品C分散均匀，接着加入2.68mL浓度为1.15×10
-2M的氯铂酸溶液，并抽真空数次排除溶液中的空气，在近红外光(λ>800nm)的条件下光照沉积5h后所得到的催化剂经7000r/min进行离心、乙醇洗涤5遍、60℃烘箱中干燥得到的样品记为PA-Ni
1.1@PCN/Pt
5hNIR。
Step 4: Add sample C to 50 mL of ultrapure water, then sonicate for 5 minutes until sample C is evenly dispersed, then add 2.68 mL of chloroplatinic acid solution with a concentration of 1.15×10 -2 M, and vacuum several times to remove the air in the solution , the catalyst obtained after illumination deposition for 5 hours under the condition of near-infrared light (λ>800nm) was centrifuged at 7000r/min, washed with ethanol 5 times, and dried in an oven at 60°C. The obtained sample was recorded as PA-Ni 1.1 @PCN/ Pt 5hNIR .
通过铂单原子/簇(Pt-SAC)促进PA-Ni/PCN光敏化体系中光生电荷的分离，从而实现在波长大于800纳米以上的光催化全分解水性能，而且连续照射48h光催化活性并没有衰减，具有很好的稳定性。Platinum single atoms/clusters (Pt-SAC) promote the separation of photogenerated charges in the PA-Ni/PCN photosensitization system, thereby achieving full photocatalytic water splitting performance at wavelengths greater than 800 nanometers, and the photocatalytic activity is maintained under continuous irradiation for 48 hours. No attenuation and very good stability.
Claims (6)
- 一种铂单原子/簇修饰的光敏化体系的制备方法，其特征在于，具体步骤如下：A method for preparing a platinum single atom/cluster modified photosensitization system, which is characterized in that the specific steps are as follows:步骤1：尿素研磨均匀放入坩埚内，然后置于马弗炉中煅烧得到样品A；Step 1: Grind the urea evenly and put it into the crucible, then place it in a muffle furnace and calcine to obtain sample A;步骤2：量取植酸溶液，向植酸溶液中加入无水乙醇，得到植酸和乙醇的混合溶液B；Step 2: Measure the phytic acid solution and add absolute ethanol to the phytic acid solution to obtain a mixed solution B of phytic acid and ethanol;步骤3：称取四水醋酸镍置于烧杯中，然后加入无水乙醇和样品A；接下来超声使得四水醋酸镍完全溶解，然后加入已配置好的植酸/乙醇的混合溶液B，搅拌、离心，乙醇洗涤，最后烘箱中烘干，得到样品C记为PA-Ni 1.1@PCN； Step 3: Weigh nickel acetate tetrahydrate into a beaker, then add absolute ethanol and sample A; then ultrasonicate to completely dissolve nickel acetate tetrahydrate, then add the prepared phytic acid/ethanol mixed solution B, and stir , centrifuge, wash with ethanol, and finally dry in an oven to obtain sample C, which is recorded as PA-Ni 1.1 @PCN;步骤4：向样品C加入超纯水，然后超声待样品C分散均匀，接着加入氯铂酸溶液，并抽真空排除溶液中的空气，在λ>800nm的近红外光条件下光照沉积5h，得到的催化剂经离心、乙醇洗涤、干燥后得到的样品为铂单原子/簇修饰的光敏化体系。Step 4: Add ultrapure water to sample C, then ultrasonic until sample C is evenly dispersed, then add chloroplatinic acid solution, vacuum to remove the air in the solution, and illuminate and deposit for 5 hours under near-infrared light conditions of λ>800nm to obtain The sample obtained after centrifuging the catalyst, washing with ethanol, and drying is a photosensitized system modified by platinum single atoms/clusters.
- 如权利要求1所述的一种铂单原子/簇修饰的光敏化体系的制备方法，其特征在于，步骤1中，所述的尿素质量为10.0g，研磨时间为5min，坩埚容量为50.0mL，升温速率为2.3℃/min，煅烧温度为550℃，煅烧时间为3h。The preparation method of a platinum single atom/cluster modified photosensitization system as claimed in claim 1, characterized in that in step 1, the mass of urea is 10.0g, the grinding time is 5min, and the crucible capacity is 50.0mL , the heating rate is 2.3℃/min, the calcination temperature is 550℃, and the calcination time is 3h.
- 如权利要求1所述的一种铂单原子/簇修饰的光敏化体系的制备方法，其特征在于，步骤2中，所述的植酸溶液的浓度为70wt％，植酸溶液与无水乙醇的体积比为1:4。The preparation method of a platinum single atom/cluster modified photosensitization system as claimed in claim 1, characterized in that in step 2, the concentration of the phytic acid solution is 70wt%, and the phytic acid solution and absolute ethanol The volume ratio is 1:4.
- 如权利要求1所述的一种铂单原子/簇修饰的光敏化体系的制备方法，其特征在于，步骤3中，所述四水醋酸镍、无水乙醇、样品A和植酸/乙醇的混合溶液B的比例为1.1mmol：50mL：200mg：25mL，超声时间为15min，搅拌时间为6h，离心转数7000r/min，洗涤5遍，烘箱温度为60℃。The preparation method of a platinum single atom/cluster modified photosensitization system as claimed in claim 1, characterized in that in step 3, the nickel acetate tetrahydrate, absolute ethanol, sample A and phytic acid/ethanol are The ratio of mixed solution B is 1.1mmol:50mL:200mg:25mL, the ultrasonic time is 15min, the stirring time is 6h, the centrifugal speed is 7000r/min, washed 5 times, and the oven temperature is 60°C.
- 如权利要求1所述的一种铂单原子/簇修饰的光敏化体系的制备方法，其特征在于，步骤4中，样品C、超纯水和氯铂酸溶液的比例为1g：50mL：2.68mL，氯铂酸溶液的浓度为1.15×10 -2M，离心转数为7000r/min，乙醇洗涤5遍，干燥温度为60℃。 The preparation method of a platinum single atom/cluster modified photosensitization system as claimed in claim 1, characterized in that in step 4, the ratio of sample C, ultrapure water and chloroplatinic acid solution is 1g:50mL:2.68 mL, the concentration of the chloroplatinic acid solution was 1.15×10 -2 M, the centrifugal speed was 7000r/min, the solution was washed 5 times with ethanol, and the drying temperature was 60°C.
- 如权利要求1-5任一所述制备方法制备的铂单原子/簇修饰的光敏化体系的用途，其特征在于，作为光催化剂用于λ>800nm的近红外光下全分解水反应。The use of the platinum single atom/cluster modified photosensitization system prepared by the preparation method according to any one of claims 1 to 5 is characterized in that it is used as a photocatalyst for complete water splitting reaction under near-infrared light with λ>800nm.
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