WO2022056979A1 - Non-metal surface plasma catalyst and preparation method and application thereof - Google Patents
Non-metal surface plasma catalyst and preparation method and application thereof Download PDFInfo
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- WO2022056979A1 WO2022056979A1 PCT/CN2020/121111 CN2020121111W WO2022056979A1 WO 2022056979 A1 WO2022056979 A1 WO 2022056979A1 CN 2020121111 W CN2020121111 W CN 2020121111W WO 2022056979 A1 WO2022056979 A1 WO 2022056979A1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/322—Volatile compounds, e.g. benzene
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- C02F2101/34—Organic compounds containing oxygen
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- C02F2103/08—Seawater, e.g. for desalination
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the invention relates to the field of photocatalytic water hydrogen production and the field of photocatalytic environmental protection, in particular to a Ti3C2(MXene)/Cd0.5Zn0.5S catalyst with a special structure assembled by non-metal surface plasmon Ti3C2(MXene) and its application in photocatalytic water (including seawater) hydrogen production, photocatalytic degradation of organic matter in water, removal of volatile organic compounds and odorous organic matter.
- Hydrogen energy as a clean and non-polluting energy source, has attracted more and more people's attention. Hydrogen has the following characteristics: good thermal conductivity, easy recovery, good combustion performance, low loss, environmental friendliness, non-corrosive product water, and high energy per unit mass.
- One of the main factors restricting the development of hydrogen energy is the high cost of hydrogen.
- the main hydrogen production methods include traditional energy hydrogen production (coal hydrogen production, natural gas hydrogen production), renewable energy hydrogen production, water electrolysis hydrogen production and industrial by-product hydrogen.
- the present invention proposes the preparation and application of a non-metallic surface plasmon Ti3C2(MXene)/Cd0.5Zn0.5S photocatalyst.
- the Cd0.5Zn0.5S photocatalyst due to the non-metallic surface plasmon Ti3C2 (MXene) extending the absorption response to sunlight, effectively separates photogenerated electrons and holes, which can strengthen the photocatalytic hydrogen production reaction.
- a preparation method of a non-metallic surface plasma catalyst comprising the following steps: dispersing Cd0.5Zn0.5S and Ti3C2 in water, then performing a hydrothermal reaction in a protective atmosphere, and washing after the reaction to obtain Ti3C2/Cd0.5Zn0 .5S, and dried to obtain a non-metallic surface plasmon catalyst.
- the content of the Ti3C2 in the catalyst is 1-7wt%.
- the content of the Ti3C2 in the catalyst is 5 ⁇ 1wt%.
- the conditions of the hydrothermal reaction are: 150-200° C. for 12-24 hours.
- the preparation of the Ti3C2 take Ti3AlC2, add hydrofluoric acid, the mass ratio of which is 1:10-200, and react for 3 to 4 days, so that the aluminum in the Ti3AlC2 is dissolved; then filter and separate, and wash until neutral. .
- the preparation of the Cd0.5Zn0.5S take equimolar zinc acetate and cadmium acetate, stir in water for 30-60 minutes, add thioacetamide and ethylenediamine, and then add enough water to carry out water Thermal reaction, the reaction conditions are 180-220 DEG C for 12-24 hours, and then washed with deionized water to obtain Cd0.5Zn0.5S.
- non-metallic surface plasmon catalyst prepared by the above method in photocatalytic water production of hydrogen, or photocatalytic degradation of organic substances in water, removal of volatile organic substances and malodorous organic substances.
- the catalyst is dispersed in water and exposed to light for at least 30 minutes; the water is fresh water or sea water.
- Na 2 SO 4 and Na 2 S are used as sacrificial agents in the photocatalytic water-to-hydrogen production, and the illumination wavelength is ⁇ 420 nm.
- the present invention has the following beneficial effects:
- Ti3C2(MXene)/Cd0.5Zn0.5S can reduce the energy required to excite electrons, and the photoresponse extends to the visible light region and the infrared light region, so the present invention proposes a non-metallic surface plasmon Ti3C2(MXene)/Cd0.
- 5Zn0.5S is used in photocatalytic water hydrogen production reaction, especially in the infrared region, it also has good activity.
- Non-metallic surface plasmon Ti3C2(MXene)/Cd0.5Zn0.5S photocatalyst used in photocatalytic water (including seawater) to produce hydrogen, degrade organic compounds in water, remove volatile organic compounds and odorous organic compounds; non-metallic surface plasmon Ti3C2 (MXene) has good electrical conductivity and can form a Schottky barrier with the surface of the semiconductor Cd0.5Zn0.5S.
- the electrons generated on the semiconductor reach the non-metallic surface plasmon Ti3C2 (MXene) through the Schotten interface, so the electrons It is enriched on the non-metal surface plasmon Ti3C2 (MXene), and the holes are enriched on the semiconductor, which inhibits the recombination of electrons and holes.
- Promote photocatalytic water (including seawater) hydrogen production reaction degrade organic compounds in water, and remove volatile organic compounds and odorous organic compounds.
- Fig. 1 is the XRD pattern of Example 1-3Cd0.5Zn0.5S, JCPDS NO.01-089-2943, Ti3C2/Cd0.5Zn0.5S.
- Figure 2 shows the photocatalytic stability of 5wt% Ti3C2/Cd0.5Zn0.5S.
- Figure 3 is the HRTEM pattern of Ti3C2, Cd0.5Zn0.5S, 5wt% Ti3C2/Cd0.5Zn0.5S.
- Figure 4 is a graph showing the effect of different proportions of Ti3C2-Cd0.5Zn0.5S on hydrogen production in seawater and freshwater, respectively.
- Figure 5 is the photocurrent spectra of different ratios of Ti3C2-Cd0.5Zn0.5S.
- Figure 6 is the impedance spectra of different ratios of Ti3C2-Cd0.5Zn0.5S.
- Figure 7 is a static-fluorescence image of different ratios of Ti3C2-Cd0.5Zn0.5S.
- Figure 8 is the effect diagram of 5wt% Ti3C2/Cd0.5Zn0.5S and the reported photocatalyst applied to hydrogen production in seawater.
- Figure 9 is a spectrum of non-metallic surface plasmon effects.
- Figure 10 is the effect diagram of the physical mixing of Ti3C2 and Cd0.5Zn0.5S and the single Cd0.5Zn0.5S hydrogen production in fresh water.
- Figure 11 is a UV diffuse reflectance map of 5% Ti3C2/Cd0.5Zn0.5S and Cd0.5Zn0.5S.
- Figure 12 is a Raman pattern of 5% Ti3C2/Cd0.5Zn0.5S and Cd0.5Zn0.5S.
- Ti3AlC2 Take 1.0 g of Ti3AlC2, add 150 ml of hydrofluoric acid, and react for 4 days to dissolve the aluminum in Ti3AlC2. It is then separated by filtration and washed with deionized water to make the washings neutral. Freeze-dried for 2 days to obtain Ti3C2 powder.
- the photocurrent spectrum of Figure 5 shows that when Ti3C2 and Cd0.5Zn0.5S are used to synthesize new materials, the photogenerated current density can be significantly increased, and a large number of electrons are generated to facilitate the photocatalytic effect.
- the impedance value is mainly determined by the exchange resistance of electrons and holes and the transfer resistance of electrons or holes.
- the reactivity of electrons and holes can be significantly improved, and the mobility of electrons or holes in the material can be improved, which is beneficial to the effect of photocatalysis.
- Figure 7 shows the static-fluorescence graph.
- the fluorescence excitation intensity can evaluate the ability of electron-hole re-polymerization inside the material.
- the tendency of electron-hole re-polymerization is obviously reduced. Thereby, it is beneficial to the effect of photocatalysis.
- Figures 7 and 5, and the experimental results in Figure 6 are consistent, which further verifies the high efficiency of the new materials synthesized by Ti3C2 and Cd0.5ZN0.5S in photocatalysis.
- the solid circle in Fig. 9 is Ti3C2.
- the plasma electric field around Ti3C2 is simulated by finite element calculation. Deepened areas all indicate a strong electric field. This figure proves that non-metallic Ti3C2 also has surface plasmon effects from the theoretical calculation and simulation.
- Figure 11 is a UV diffuse reflectance map to demonstrate that the as-synthesized 5%Ti3C2/Cd0.5Zn0.5S and Cd0.5zn0.5S still have spectral absorption starting from a wavelength of about 510 nm. ability.
- the upward trajectory of the 5%Ti3C2/Cd0.5Zn0.5S spectrum shows an obvious surface plasmon phenomenon compared to the downward trajectory of the Cd0.5Zn0.5S spectrum.
- Figure 12 is the comparison of the Raman spectra of the two. Because the surface plasmon has the effect of Raman enhancement, the newly synthesized 5%Ti3C2/Cd0.5Zn0.5S has a stronger Raman phenomenon than Cd0.5Zn0.5S .
- Example 4 Photocatalytic hydrogen production from water with different percentages of Ti3C2(MXene)/Cd0.5Zn0.5S
- GC7900 online gas chromatograph
- Example 5 Photocatalytic hydrogen production from seawater by Ti3C2(MXene)/Cd0.5Zn0.5S
- Example 6 Photocatalytic degradation of organic matter in water by Ti3C2(MXene)/Cd0.5Zn0.5S
- Example 7 Photocatalytic removal of volatile organic compounds and malodorous organic compounds by Ti3C2(MXene)/Cd0.5Zn0.5S
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Abstract
The present invention relates to the field of photocatalytic hydrogen production from water and the field of photocatalytic environmental protection. Disclosed are a non-metal surface plasma catalyst, and a preparation method and an application thereof. The preparation method comprises the following steps: dispersing Cd0.5Zn0.5S and Ti3C2 in water, then performing a hydrothermal reaction in a protective atmosphere, washing after the reaction is finished to obtain Ti3C2/Cd0.5Zn0.5S, and drying to obtain the non-metal surface plasma catalyst. The catalyst in the present invention is applied to photocatalytic hydrogen production from water (comprising seawater), degradation of organic matters in water and removal of volatile organic matters and foul organic matters, and has the advantages of being wide in a photoresponse range, being capable of effectively separating photo-induced electrons and hole pairs, and having high photocatalytic activity.
Description
本发明涉及光催化水制氢领域和光催化环保领域，具体地涉及一种具有非金属表面等离子体Ti3C2(MXene)组装特殊结构的Ti3C2(MXene)/Cd0.5Zn0.5S催化剂及其在光催化水(包括海水)制氢，光催化降解水中有机物,去除挥发性有机物和恶臭有机物中的应用。The invention relates to the field of photocatalytic water hydrogen production and the field of photocatalytic environmental protection, in particular to a Ti3C2(MXene)/Cd0.5Zn0.5S catalyst with a special structure assembled by non-metal surface plasmon Ti3C2(MXene) and its application in photocatalytic water (including seawater) hydrogen production, photocatalytic degradation of organic matter in water, removal of volatile organic compounds and odorous organic matter.
环境和可再生资源利用是人类生存在地球上的挑战，不断增加的温室气体排放和清洁能源成为全球经济和气候尚未解决的问题。为了人类可持续发展的需要，应综合利用资源，保护环境，与自然和谐相处；化石能源短缺和全球环境问题需要迫切解决。氢能，作为一种清洁无污染的能源，已经受到越来越多人的关注。氢气具有以下特点：导热好、易回收、燃烧性能好、损耗小，对环境友好，产物水无腐蚀性，单位质量的能量很高。当前制约氢能发展的主要因素之一在于氢气费用高。目前主要的氢气生产方法包括传统能源制氢(煤制氢、天然气制氢)，可再生能源制氢，水电解制氢及工业副产氢。煤气化制氢，经济成本/CNY·(kgH
2)：8.3～19.5CNY/kgH
2；能耗：190～325MJ/kgH
2；温室气体释放：5000～11300gCO
2/kgH
2。天然气制氢，经济成本/CNY·(kgH
2)：10.4～27.6CNY/kgH
2；能耗：165～360MJ/kgH
2；温室气体释放：8400gCO
2/kgH
2。热化学制氢，经济成本/CNY·(kgH
2)：12.8～36.9CNY/kgH
2；能耗：360～410MJ/kgH
2；温室气体释放：360g～860gCO
2/kgH
2。可再生能源发电制氢，(风电制氢)经济成本/CNY·(kgH
2)：22.3～59.8CNY/kgH
2；能耗：9～12MJ/kgH
2；温室气体释放：785gCO
2/kgH
2。(太阳能光伏发电制氢)经济成本/CNY·(kgH
2)：36.6～61.3CNY/kgH
2；能耗：30～80MJ/kgH
2；温室 气体释放：4600gCO
2/kgH
2。生物质气化制氢，经济成本/CNY·(kgH
2)：9.7～22.2CNY/kgH
2；能耗：4～20MJ/kgH
2；温室气体释放：3000g CO
2/kgH
2。传统的制氢方法碳氢化合物蒸汽重整，电解水和重油氧化生成氢气,能耗和转化过程中的有害物质产生限制了友好氢能资源的开发。因此，通过太阳能将水转化为氢气被认为是有希望的解决这些问题的方法。光催化水制氢过程的由于光生电子和空穴的复合，使得制氢产量不高；光催化剂对太阳光谱吸收响应窄，太阳能利用不足。设计光催化剂应具有广泛的光响应范围，并且可以有效抑制光生电子-空穴的复合。另一方面，地球上的水资源97％是被海水覆盖，如果能够使得光催化水制备氢气的应用范围扩大到海水领域将会有十分重要的意义。于此同时，基于太阳能光催化生成电子-空穴对的原理，其在水中有机物降解，去除挥发性有机物和恶臭有机物也有明显的效果。
The environment and the utilization of renewable resources are the challenges for human beings to survive on the earth, and the ever-increasing greenhouse gas emissions and clean energy have become unresolved issues for the global economy and climate. In order to meet the needs of sustainable human development, resources should be comprehensively utilized, the environment should be protected, and nature should be in harmony; the shortage of fossil energy and global environmental problems need to be urgently resolved. Hydrogen energy, as a clean and non-polluting energy source, has attracted more and more people's attention. Hydrogen has the following characteristics: good thermal conductivity, easy recovery, good combustion performance, low loss, environmental friendliness, non-corrosive product water, and high energy per unit mass. One of the main factors restricting the development of hydrogen energy is the high cost of hydrogen. At present, the main hydrogen production methods include traditional energy hydrogen production (coal hydrogen production, natural gas hydrogen production), renewable energy hydrogen production, water electrolysis hydrogen production and industrial by-product hydrogen. Coal gasification for hydrogen production, economic cost/CNY·(kgH 2 ): 8.3～19.5CNY/kgH 2 ; energy consumption: 190～325MJ/kgH 2 ; greenhouse gas release: 5000～11300gCO 2 /kgH 2 . Hydrogen production from natural gas, economic cost/CNY·(kgH 2 ): 10.4～27.6CNY/kgH 2 ; energy consumption: 165～360MJ/kgH 2 ; greenhouse gas release: 8400gCO 2 /kgH 2 . Thermochemical hydrogen production, economic cost/CNY·(kgH 2 ): 12.8～36.9CNY/kgH 2 ; energy consumption: 360～410MJ/kgH 2 ; greenhouse gas release: 360g～860gCO 2 /kgH 2 . Hydrogen production from renewable energy power generation, (wind power hydrogen production) economic cost/CNY·(kgH 2 ): 22.3～59.8CNY/kgH 2 ; energy consumption: 9～12MJ/kgH 2 ; greenhouse gas release: 785gCO 2 /kgH 2 . (Hydrogen production by solar photovoltaic power generation) Economic cost/CNY·(kgH 2 ): 36.6-61.3 CNY/kgH 2 ; energy consumption: 30-80 MJ/kgH 2 ; greenhouse gas release: 4600gCO 2 /kgH 2 . Biomass gasification for hydrogen production, economic cost/CNY·(kgH 2 ): 9.7～22.2CNY/kgH 2 ; energy consumption: 4～20MJ/kgH 2 ; greenhouse gas release: 3000g CO 2 /kgH 2 . Traditional hydrogen production methods include steam reforming of hydrocarbons, electrolysis of water and oxidation of heavy oil to generate hydrogen, energy consumption and the generation of harmful substances in the conversion process, which limit the development of friendly hydrogen energy resources. Therefore, converting water to hydrogen via solar energy is considered a promising solution to these problems. Due to the recombination of photogenerated electrons and holes in the photocatalytic water hydrogen production process, the hydrogen production yield is not high; the photocatalyst has a narrow absorption response to the solar spectrum, and the utilization of solar energy is insufficient. The designed photocatalyst should have a broad photoresponse range and can effectively suppress the photogenerated electron-hole recombination. On the other hand, 97% of the water resources on the earth are covered by sea water. It will be of great significance to expand the application of photocatalytic water for hydrogen production to the sea water field. At the same time, based on the principle of solar photocatalysis to generate electron-hole pairs, it also has obvious effects on the degradation of organic compounds in water and the removal of volatile organic compounds and malodorous organic compounds.
发明内容SUMMARY OF THE INVENTION
针对现有技术的不足，本发明提出了一种非金属表面等离子体Ti3C2(MXene)/Cd0.5Zn0.5S光催化剂的制备及其应用，本发明采用组装非金属表面等离子体Ti3C2(MXene)/Cd0.5Zn0.5S光催化剂，由于非金属表面等离子体Ti3C2(MXene)扩展了对太阳光的吸收响应，有效地使光生电子-空穴分离，可以强化光催化制氢反应。In view of the deficiencies of the prior art, the present invention proposes the preparation and application of a non-metallic surface plasmon Ti3C2(MXene)/Cd0.5Zn0.5S photocatalyst. The Cd0.5Zn0.5S photocatalyst, due to the non-metallic surface plasmon Ti3C2 (MXene) extending the absorption response to sunlight, effectively separates photogenerated electrons and holes, which can strengthen the photocatalytic hydrogen production reaction.
为了实现上述目的，本发明采用的技术方案如下：In order to achieve the above object, the technical scheme adopted in the present invention is as follows:
一种非金属表面等离子体催化剂的制备方法，包括如下步骤：将Cd0.5Zn0.5S和Ti3C2分散在水中，然后，在保护气氛下进行水热反应，反应结束后洗涤，得到Ti3C2/Cd0.5Zn0.5S，干燥，获得非金属表面等离子体催化剂。A preparation method of a non-metallic surface plasma catalyst, comprising the following steps: dispersing Cd0.5Zn0.5S and Ti3C2 in water, then performing a hydrothermal reaction in a protective atmosphere, and washing after the reaction to obtain Ti3C2/Cd0.5Zn0 .5S, and dried to obtain a non-metallic surface plasmon catalyst.
优选地，所述Ti3C2在催化剂中的含量为1～7wt％。Preferably, the content of the Ti3C2 in the catalyst is 1-7wt%.
优选地，所述Ti3C2在催化剂中的含量为5±1wt％。Preferably, the content of the Ti3C2 in the catalyst is 5±1wt%.
优选地，所述水热反应的条件为：150～200℃反应12～24小时。Preferably, the conditions of the hydrothermal reaction are: 150-200° C. for 12-24 hours.
优选地，所述Ti3C2的制备：取Ti3AlC2，加入氢氟酸，其质量比为1：10-200，反应3～4天，使得Ti3AlC2中的铝溶出；然后过滤分离，洗涤至中性即可。Preferably, the preparation of the Ti3C2: take Ti3AlC2, add hydrofluoric acid, the mass ratio of which is 1:10-200, and react for 3 to 4 days, so that the aluminum in the Ti3AlC2 is dissolved; then filter and separate, and wash until neutral. .
优选地，所述Cd0.5Zn0.5S的制备：取等摩尔的醋酸锌和醋酸镉，于水中搅拌30～60分钟，加入硫代乙酰胺和乙二胺，随后加入足量的水，进行水热反应，反应条件为180～220℃反应12～24小时，然后用去离子水洗涤，得到Cd0.5Zn0.5S。Preferably, the preparation of the Cd0.5Zn0.5S: take equimolar zinc acetate and cadmium acetate, stir in water for 30-60 minutes, add thioacetamide and ethylenediamine, and then add enough water to carry out water Thermal reaction, the reaction conditions are 180-220 DEG C for 12-24 hours, and then washed with deionized water to obtain Cd0.5Zn0.5S.
上述方法制得的非金属表面等离子体催化剂在光催化水制氢，或者光催化降解水中有机物、去除挥发性有机物和恶臭有机物中的应用。The application of the non-metallic surface plasmon catalyst prepared by the above method in photocatalytic water production of hydrogen, or photocatalytic degradation of organic substances in water, removal of volatile organic substances and malodorous organic substances.
优选地，所述光催化水制氢是将催化剂分散于水中，光照至少30min；所述水为淡水或海水。Preferably, in the photocatalytic water production of hydrogen, the catalyst is dispersed in water and exposed to light for at least 30 minutes; the water is fresh water or sea water.
优选地，所述光催化水制氢用Na
2SO
4和Na
2S作为牺牲剂，光照波长≥420nm。
Preferably, Na 2 SO 4 and Na 2 S are used as sacrificial agents in the photocatalytic water-to-hydrogen production, and the illumination wavelength is ≥420 nm.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1.与光催化剂Cd0.5Zn0.5S相比，具有非金属表面等离子体作用，有效分离光生电子-空穴，极大地提高了光催化活性。1. Compared with the photocatalyst Cd0.5Zn0.5S, it has the effect of non-metal surface plasmon, effectively separates photogenerated electrons and holes, and greatly improves the photocatalytic activity.
2.Ti3C2(MXene)/Cd0.5Zn0.5S耦合可以使得激发电子所需能量减小，光响应扩展到可见光区和红外光区，则本发明提出非金属表面等离子体Ti3C2(MXene)/Cd0.5Zn0.5S应用于光催化水制氢反应，尤其是在红外区也有较好的活性。2. The coupling of Ti3C2(MXene)/Cd0.5Zn0.5S can reduce the energy required to excite electrons, and the photoresponse extends to the visible light region and the infrared light region, so the present invention proposes a non-metallic surface plasmon Ti3C2(MXene)/Cd0. 5Zn0.5S is used in photocatalytic water hydrogen production reaction, especially in the infrared region, it also has good activity.
3.非金属表面等离子体Ti3C2(MXene)/Cd0.5Zn0.5S光催化剂，形成的肖特基势垒相互协同作用有利于增强光催化活性。3. The non-metallic surface plasmon Ti3C2(MXene)/Cd0.5Zn0.5S photocatalyst, the Schottky barrier formed synergistically is beneficial to enhance the photocatalytic activity.
4.非金属表面等离子体Ti3C2(MXene)/Cd0.5Zn0.5S光催化剂，应用于光催化水(包括海水)产氢,降解水中有机物,去除挥发性有机物和恶臭有机物；非金属表面等离子体Ti3C2(MXene)具有较好的导电性，可以和半导体Cd0.5Zn0.5S表面形成肖特基势垒，在半导体上产生的电子经肖特恩界面到达非金属表面等离子体Ti3C2(MXene)，所 以电子在非金属表面等离子体Ti3C2(MXene)上富集，空穴在半导体上富集，抑制电子和空穴的复合。促进光催化水(包括海水)制氢反应，降解水中的有机物,去除挥发性有机物和恶臭有机物。4. Non-metallic surface plasmon Ti3C2(MXene)/Cd0.5Zn0.5S photocatalyst, used in photocatalytic water (including seawater) to produce hydrogen, degrade organic compounds in water, remove volatile organic compounds and odorous organic compounds; non-metallic surface plasmon Ti3C2 (MXene) has good electrical conductivity and can form a Schottky barrier with the surface of the semiconductor Cd0.5Zn0.5S. The electrons generated on the semiconductor reach the non-metallic surface plasmon Ti3C2 (MXene) through the Schotten interface, so the electrons It is enriched on the non-metal surface plasmon Ti3C2 (MXene), and the holes are enriched on the semiconductor, which inhibits the recombination of electrons and holes. Promote photocatalytic water (including seawater) hydrogen production reaction, degrade organic compounds in water, and remove volatile organic compounds and odorous organic compounds.
图1是实施例1-3Cd0.5Zn0.5S，JCPDSNO.01-089-2943、Ti3C2/Cd0.5Zn0.5S的XRD图谱。Fig. 1 is the XRD pattern of Example 1-3Cd0.5Zn0.5S, JCPDS NO.01-089-2943, Ti3C2/Cd0.5Zn0.5S.
图2是5wt％Ti3C2/Cd0.5Zn0.5S光催化稳定性。Figure 2 shows the photocatalytic stability of 5wt% Ti3C2/Cd0.5Zn0.5S.
图3是Ti3C2，Cd0.5Zn0.5S，5wt％Ti3C2/Cd0.5Zn0.5S的HRTEM图谱。Figure 3 is the HRTEM pattern of Ti3C2, Cd0.5Zn0.5S, 5wt% Ti3C2/Cd0.5Zn0.5S.
图4是不同比例Ti3C2-Cd0.5Zn0.5S分别在海水和淡水中产氢的效果图。Figure 4 is a graph showing the effect of different proportions of Ti3C2-Cd0.5Zn0.5S on hydrogen production in seawater and freshwater, respectively.
图5是不同比例Ti3C2-Cd0.5Zn0.5S的光电流谱图。Figure 5 is the photocurrent spectra of different ratios of Ti3C2-Cd0.5Zn0.5S.
图6是不同比例Ti3C2-Cd0.5Zn0.5S的阻抗谱图。Figure 6 is the impedance spectra of different ratios of Ti3C2-Cd0.5Zn0.5S.
图7是不同比例Ti3C2-Cd0.5Zn0.5S的静态-荧光图。Figure 7 is a static-fluorescence image of different ratios of Ti3C2-Cd0.5Zn0.5S.
图8是5wt％Ti3C2/Cd0.5Zn0.5S与已经报道的光催化剂应用于海水中产氢的效果图。Figure 8 is the effect diagram of 5wt% Ti3C2/Cd0.5Zn0.5S and the reported photocatalyst applied to hydrogen production in seawater.
图9是非金属表面等离子体效应的谱图。Figure 9 is a spectrum of non-metallic surface plasmon effects.
图10是Ti3C2和Cd0.5Zn0.5S物理混合、单独Cd0.5Zn0.5S在淡水中产氢的效果图。Figure 10 is the effect diagram of the physical mixing of Ti3C2 and Cd0.5Zn0.5S and the single Cd0.5Zn0.5S hydrogen production in fresh water.
图11是5％Ti3C2/Cd0.5Zn0.5S和Cd0.5Zn0.5S的UV漫反射图。Figure 11 is a UV diffuse reflectance map of 5% Ti3C2/Cd0.5Zn0.5S and Cd0.5Zn0.5S.
图12是5％Ti3C2/Cd0.5Zn0.5S和Cd0.5Zn0.5S的拉曼图谱。Figure 12 is a Raman pattern of 5% Ti3C2/Cd0.5Zn0.5S and Cd0.5Zn0.5S.
以下结合附图和具体实施例对本发明作具体的介绍，但不限定本发明的保护范围。The present invention is described in detail below with reference to the accompanying drawings and specific embodiments, but does not limit the protection scope of the present invention.
实施例1：制备Cd0.5Zn0.5S粉体Example 1: Preparation of Cd0.5Zn0.5S powder
取等摩尔的醋酸锌和醋酸镉，于去离子水中搅拌60分钟，加入硫代乙酰胺和乙二胺，随后加入足够的去离子水，转入高压釜中水热反 应，在180℃条件下，反应12小时，在常温下，用去离子水洗涤，然后冻干，得到Cd0.5Zn0.5S粉粒。Take equimolar zinc acetate and cadmium acetate, stir in deionized water for 60 minutes, add thioacetamide and ethylenediamine, then add enough deionized water, transfer to the autoclave for hydrothermal reaction, under the condition of 180 ℃ , reacted for 12 hours, washed with deionized water at room temperature, and then freeze-dried to obtain Cd0.5Zn0.5S powder.
实施例2：制备Ti3C2粉体Example 2: Preparation of Ti3C2 powder
取1.0gTi3AlC2，加入氢氟酸150毫升，反应4天，使得Ti3AlC2中的铝溶出。然后过滤分离，用去离子水洗涤分离，使洗涤液成为中性。冻干2天，得到Ti3C2粉末。Take 1.0 g of Ti3AlC2, add 150 ml of hydrofluoric acid, and react for 4 days to dissolve the aluminum in Ti3AlC2. It is then separated by filtration and washed with deionized water to make the washings neutral. Freeze-dried for 2 days to obtain Ti3C2 powder.
实施例3：制备非金属表面等离子体Ti3C2(MXene)/Cd0.5Zn0.5S光催化剂Example 3: Preparation of non-metallic surface plasmonic Ti3C2(MXene)/Cd0.5Zn0.5S photocatalyst
将0.05g的Cd0.5Zn0.5S溶于40mL脱氧去离子水中，然后，加入适量的Ti3C2水溶液中，在氩气条件保护下搅拌2小时；然后，在水热条件下，200℃反应24小时，在常温下，用去离子水洗涤，得到Ti3C2(MXene)/Cd0.5Zn0.5S粉体，真空干燥24小时，获得用于光催化的催化剂。调控Ti3C2的比例获得Ti3C2含量分别为1wt％、3wt％、5wt％和7wt％的Ti3C2/Cd0.5Zn0.5S光催化剂。Dissolve 0.05 g of Cd0.5Zn0.5S in 40 mL of deoxygenated deionized water, add an appropriate amount of Ti3C2 aqueous solution, and stir for 2 hours under argon protection; then, under hydrothermal conditions, react at 200 °C for 24 hours, At room temperature, washed with deionized water to obtain Ti3C2(MXene)/Cd0.5Zn0.5S powder, and vacuum dried for 24 hours to obtain a catalyst for photocatalysis. By adjusting the ratio of Ti3C2, Ti3C2/Cd0.5Zn0.5S photocatalysts with Ti3C2 contents of 1wt%, 3wt%, 5wt% and 7wt% were obtained, respectively.
图5的光电流谱图，当有Ti3C2和Cd0.5Zn0.5S合成新材料时，可以明显提升其光生电流密度，大量的电子产生利于光催化的效果。The photocurrent spectrum of Figure 5 shows that when Ti3C2 and Cd0.5Zn0.5S are used to synthesize new materials, the photogenerated current density can be significantly increased, and a large number of electrons are generated to facilitate the photocatalytic effect.
图6的阻抗谱图，阻抗值大小主要由电子-空穴的交换电阻以及自身的电子或空穴迁移电阻决定的。当有ti3C2和Cd0.5Zn0.5S合成新材料时，可以明显改善电子-空穴的反应能力，同时提高电子或空穴在材料内的迁移能力，从而有利于光催化的效果。As shown in the impedance spectrum of FIG. 6 , the impedance value is mainly determined by the exchange resistance of electrons and holes and the transfer resistance of electrons or holes. When a new material is synthesized with ti3C2 and Cd0.5Zn0.5S, the reactivity of electrons and holes can be significantly improved, and the mobility of electrons or holes in the material can be improved, which is beneficial to the effect of photocatalysis.
图7的静态-荧光图，荧光激发强度可以评价材料内部电子-空穴重新聚合的能力，当Ti3C2和Cd0.5Zn0.5S合成新材料时，明显的降低了电子-空穴重新聚合的趋势，从而有利于光催化的效果。图7和图5，图6的实验结果都是相符合的，进一步的验证了Ti3C2和Cd0.5ZN0.5S合成的新材料在光催化方面的高效性。Figure 7 shows the static-fluorescence graph. The fluorescence excitation intensity can evaluate the ability of electron-hole re-polymerization inside the material. When Ti3C2 and Cd0.5Zn0.5S synthesize new materials, the tendency of electron-hole re-polymerization is obviously reduced. Thereby, it is beneficial to the effect of photocatalysis. Figures 7 and 5, and the experimental results in Figure 6 are consistent, which further verifies the high efficiency of the new materials synthesized by Ti3C2 and Cd0.5ZN0.5S in photocatalysis.
图9中的实心圆是Ti3C2，当有光辐射时通过有限元的计算模拟Ti3C2周围的等离子体电场。加深的区域都是表示有很强的电场。这 张图从理论计算模拟的方面证明非金属性的Ti3C2也具有表面等离子体效应。The solid circle in Fig. 9 is Ti3C2. When there is light radiation, the plasma electric field around Ti3C2 is simulated by finite element calculation. Deepened areas all indicate a strong electric field. This figure proves that non-metallic Ti3C2 also has surface plasmon effects from the theoretical calculation and simulation.
图11是UV漫反射图以证明合成的5％Ti3C2/Cd0.5Zn0.5S和Cd0.5zn0.5S比较而言，从大约510纳米的波长开始5％Ti3C2/Cd0.5Zn0.5S仍然有着光谱吸收能力。5％Ti3C2/Cd0.5Zn0.5S图谱上扬的轨迹相对Cd0.5Zn0.5S图谱下垂的轨迹展示着明显的表面等离子体现象。图12是这两者的拉曼图谱的对比，因为表面等离子有着拉曼增强的效果，所以新合成的5％Ti3C2/Cd0.5Zn0.5S相对于Cd0.5Zn0.5S有着较强的拉曼现象。Figure 11 is a UV diffuse reflectance map to demonstrate that the as-synthesized 5%Ti3C2/Cd0.5Zn0.5S and Cd0.5zn0.5S still have spectral absorption starting from a wavelength of about 510 nm. ability. The upward trajectory of the 5%Ti3C2/Cd0.5Zn0.5S spectrum shows an obvious surface plasmon phenomenon compared to the downward trajectory of the Cd0.5Zn0.5S spectrum. Figure 12 is the comparison of the Raman spectra of the two. Because the surface plasmon has the effect of Raman enhancement, the newly synthesized 5%Ti3C2/Cd0.5Zn0.5S has a stronger Raman phenomenon than Cd0.5Zn0.5S .
实施例4：不同百分比的Ti3C2(MXene)/Cd0.5Zn0.5S光催化水制氢Example 4: Photocatalytic hydrogen production from water with different percentages of Ti3C2(MXene)/Cd0.5Zn0.5S
取50毫克1～7wt％Ti3C2/Cd0.5Zn0.5S粉体分散于70毫升去离子水中，用0.25MNa
2SO
4和0.35MNa
2S作为牺牲剂，在氮气条件下，光源为300W氙灯光照1h，每小时取样在线气相色谱仪(GC7900,TCD检测器；
分子筛，氮气作为载气)检测产氢情况，效果详见图4，其中5wt％的Ti3C2/Cd0.5Zn0.5S的产氢效率达到14mmol/g/h。
Disperse 50 mg of 1-7wt% Ti3C2/ Cd0.5Zn0.5S powder in 70 ml of deionized water, use 0.25MNa2SO4 and 0.35MNa2S as sacrificial agents, under nitrogen conditions, the light source is 300W xenon light for 1h , Hourly sampling online gas chromatograph (GC7900, TCD detector; Molecular sieve, nitrogen as carrier gas) to detect hydrogen production, the effect is shown in Figure 4, in which the hydrogen production efficiency of 5wt% Ti3C2/Cd0.5Zn0.5S reaches 14mmol/g/h.
实施例5：Ti3C2(MXene)/Cd0.5Zn0.5S光催化海水制氢Example 5: Photocatalytic hydrogen production from seawater by Ti3C2(MXene)/Cd0.5Zn0.5S
取50毫克1～7wt％Ti3C2/Cd0.5Zn0.5S粉体分散于70毫升海水中，用0.25MNa2SO4和0.35MNa2S作为牺牲剂，在氮气条件下，光源为300W氙灯光照1h，每小时取样在线气相色谱仪(GC7900,TCD检测器；
分子筛，氮气作为载气)检测产氢情况，效果详见图4，其中5wt％的Ti3C2/Cd0.5Zn0.5S的产氢效率达到9mmol/g/h。
Disperse 50 mg of 1-7wt% Ti3C2/Cd0.5Zn0.5S powder in 70 ml of seawater, use 0.25MNa2SO4 and 0.35MNa2S as sacrificial agents, under nitrogen conditions, the light source is 300W xenon light for 1h, and the online gas phase is sampled every hour Chromatograph (GC7900, TCD detector; Molecular sieve, nitrogen as carrier gas) to detect hydrogen production, the effect is shown in Figure 4, in which the hydrogen production efficiency of 5wt% Ti3C2/Cd0.5Zn0.5S reaches 9mmol/g/h.
从图8可见，本发明5wt％Ti3C2/Cd0.5Zn0.5S催化剂的产氢量远高于现有催化剂。It can be seen from FIG. 8 that the hydrogen production of the 5wt% Ti3C2/Cd0.5Zn0.5S catalyst of the present invention is much higher than that of the existing catalyst.
Ti3C2和Cd0.5Zn0.5S的物理混合后的光催化效果详见图10，说明了简单的加成混合并不能达到增强性的光催化效果。Ti3C2-Cd0.5Zn0.5S只有经过本发明方法制备才能达到比较好的光催 化效果。The photocatalytic effect after physical mixing of Ti3C2 and Cd0.5Zn0.5S is shown in Figure 10, which shows that simple addition and mixing cannot achieve enhanced photocatalytic effect. Only when Ti3C2-Cd0.5Zn0.5S is prepared by the method of the present invention, a better photocatalytic effect can be achieved.
实施例6：Ti3C2(MXene)/Cd0.5Zn0.5S光催化降解水中有机物Example 6: Photocatalytic degradation of organic matter in water by Ti3C2(MXene)/Cd0.5Zn0.5S
取50毫克5wt％Ti3C2/Cd0.5Zn0.5S粉体于70毫升分别含有10mg/L浓度的环丙沙星，甲基橙，双酚A溶液中，以光源为300W Xenon lamp光照，每2分钟取样以高效液相色谱检测配置溶液中有机物的浓度以确定光催化降解的效果。所有被测有机物的降解效率在较短时间(2min)内都超过90％以上，其中降解效率：环丙沙星为93.23％，甲基橙为94.87％，双酚A为96.75％。Take 50 mg of 5wt% Ti3C2/Cd0.5Zn0.5S powder in 70 ml of ciprofloxacin, methyl orange and bisphenol A solution with a concentration of 10 mg/L respectively. Sampling was used to detect the concentration of organic matter in the prepared solution by high performance liquid chromatography to determine the effect of photocatalytic degradation. The degradation efficiency of all tested organics exceeded 90% in a short time (2min), among which the degradation efficiency was 93.23% for ciprofloxacin, 94.87% for methyl orange and 96.75% for bisphenol A.
实施例7：Ti3C2(MXene)/Cd0.5Zn0.5S光催化去除挥发性有机物和恶臭有机物Example 7: Photocatalytic removal of volatile organic compounds and malodorous organic compounds by Ti3C2(MXene)/Cd0.5Zn0.5S
取50毫克5wt％Ti3C2(MXene)/Cd0.5Zn0.5S粉体置于密闭容器中分别通入氯代烃,甲苯，甲醛气体使得已经抽真空预处理的密闭容器内挥发有机物和恶臭有机物的浓度控制在200ppb，以光源为300W Xenon lamp光照，以气相色谱在线自动取样检测容器内中有机物的浓度以确定光催化去除挥发性有机物和恶臭有机物的效果。所有被测有机物的去除效率在较短时间(10min)内都超过80％以上(氯代烃83.98％，甲苯89.15％，甲醛86.49％)。Take 50 mg of 5wt% Ti3C2(MXene)/Cd0.5Zn0.5S powder and put it in a closed container, respectively, and pass chlorinated hydrocarbons, toluene, and formaldehyde gas into the closed container that has been vacuum pretreated to make the concentration of volatile organic compounds and malodorous organic compounds. Controlled at 200ppb, the light source is 300W Xenon lamp illumination, and the concentration of organic substances in the container is automatically sampled and detected by gas chromatography to determine the effect of photocatalytic removal of volatile organic compounds and malodorous organic compounds. The removal efficiency of all tested organics exceeded 80% in a short time (10min) (chlorinated hydrocarbons 83.98%, toluene 89.15%, formaldehyde 86.49%).
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, The simplification should be equivalent replacement manners, which are all included in the protection scope of the present invention.
Claims (10)
- 一种非金属表面等离子体催化剂的制备方法，其特征在于，包括如下步骤：A preparation method of a non-metallic surface plasma catalyst is characterized in that, comprises the following steps:将Cd0.5Zn0.5S和Ti3C2分散在水中，然后，在保护气氛下进行水热反应，反应结束后洗涤，得到Ti3C2/Cd0.5Zn0.5S，干燥，获得非金属表面等离子体催化剂。Disperse Cd0.5Zn0.5S and Ti3C2 in water, then perform hydrothermal reaction under protective atmosphere, wash after reaction to obtain Ti3C2/Cd0.5Zn0.5S, and dry to obtain non-metallic surface plasmon catalyst.
- 根据权利要求1所述的制备方法，其特征在于，所述Ti3C2在催化剂中的含量为1～7wt％。The preparation method according to claim 1, wherein the content of the Ti3C2 in the catalyst is 1-7wt%.
- 根据权利要求2所述的制备方法，其特征在于，所述Ti3C2在催化剂中的含量为5±1wt％。The preparation method according to claim 2, wherein the content of the Ti3C2 in the catalyst is 5±1wt%.
- 根据权利要求1或2或3所述的制备方法，其特征在于，所述水热反应的条件为：150～200℃反应12～24小时。The preparation method according to claim 1, 2 or 3, characterized in that, the conditions of the hydrothermal reaction are: 150-200°C for 12-24 hours.
- 根据权利要求1或2或3所述的制备方法，其特征在于，所述Ti3C2的制备：取Ti3AlC2，加入氢氟酸，其质量比为1：10-200，反应3～4天，使得Ti3AlC2中的铝溶出；然后过滤分离，洗涤至中性即可。The preparation method according to claim 1, 2 or 3, characterized in that, the preparation of Ti3C2: take Ti3AlC2, add hydrofluoric acid, the mass ratio of which is 1:10-200, and react for 3 to 4 days, so that Ti3AlC2 The aluminum in the solution is dissolved; then it is separated by filtration and washed to neutrality.
- 根据权利要求1或2或3所述的制备方法，其特征在于，所述Cd0.5Zn0.5S的制备：取等摩尔的醋酸锌和醋酸镉，于水中搅拌30～60分钟，加入硫代乙酰胺和乙二胺，随后加入足量的水，进行水热反应，反应条件为180～220℃反应12～24小时，然后用去离子水洗涤，得到Cd0.5Zn0.5S。The preparation method according to claim 1, 2 or 3, wherein the preparation of the Cd0.5Zn0.5S: take equimolar zinc acetate and cadmium acetate, stir in water for 30-60 minutes, add thioethyl Amide and ethylenediamine, and then add enough water to carry out hydrothermal reaction, the reaction condition is 180～220℃ for 12～24 hours, and then washed with deionized water to obtain Cd0.5Zn0.5S.
- 权利要求1～6任意一项所述方法制得的非金属表面等离子体催化剂。The non-metallic surface plasmon catalyst prepared by the method of any one of claims 1 to 6.
- 权利要求7所述非金属表面等离子体催化剂在光催化水制氢，或者光催化降解水中有机物、去除挥发性有机物和恶臭有机物中的应用。The application of the non-metallic surface plasmon catalyst of claim 7 in photocatalytic water production of hydrogen, or photocatalytic degradation of organic matter in water, removal of volatile organic matter and malodorous organic matter.
- 根据权利要求8所述的应用，其特征在于，所述光催化水制氢 是将催化剂分散于水中，光照至少30min；所述水为淡水或海水。Application according to claim 8, is characterized in that, described photocatalytic water hydrogen production is to disperse catalyst in water, illumination at least 30min; Described water is fresh water or seawater.
- 根据权利要求9所述的应用，其特征在于，所述光催化水制氢用Na 2SO 4和Na 2S作为牺牲剂，光照波长≥420nm。 The application according to claim 9, wherein the photocatalytic hydrogen production from water uses Na 2 SO 4 and Na 2 S as sacrificial agents, and the illumination wavelength is greater than or equal to 420 nm.
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