CN110075875A - 一种以NiSe为助剂的高效异质结光催化剂及其制备方法和应用 - Google Patents
一种以NiSe为助剂的高效异质结光催化剂及其制备方法和应用 Download PDFInfo
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- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 title description 3
- 239000011701 zinc Substances 0.000 claims abstract description 74
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000006104 solid solution Substances 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims abstract description 10
- 230000036571 hydration Effects 0.000 claims abstract description 10
- 238000006703 hydration reaction Methods 0.000 claims abstract description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 10
- 229960001471 sodium selenite Drugs 0.000 claims abstract description 10
- 239000011781 sodium selenite Substances 0.000 claims abstract description 10
- 235000015921 sodium selenite Nutrition 0.000 claims abstract description 10
- 238000007146 photocatalysis Methods 0.000 claims abstract description 7
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004246 zinc acetate Substances 0.000 claims abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000005864 Sulphur Substances 0.000 claims abstract 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052793 cadmium Inorganic materials 0.000 claims abstract 2
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims abstract 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract 2
- 229910052725 zinc Inorganic materials 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
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- 238000006243 chemical reaction Methods 0.000 claims description 7
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- 238000000034 method Methods 0.000 abstract description 4
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- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 8
- 238000006303 photolysis reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
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- 238000000926 separation method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- AUIZLSZEDUYGDE-UHFFFAOYSA-L cadmium(2+);diacetate;dihydrate Chemical compound O.O.[Cd+2].CC([O-])=O.CC([O-])=O AUIZLSZEDUYGDE-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical class [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 nickelous selenides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
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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
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- B01J35/39—Photocatalytic properties
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- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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- 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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Abstract
本发明公开了一种可见光驱动的高效光催化水裂解产氢的NiSe基异质结光催化剂,首先以醋酸镉、醋酸锌和硫代乙酰胺分别作为镉、锌和硫源,采用沉淀‑水热法制备了Cd0.5Zn0.5S固溶体,接着以六水合硫酸镍、亚硒酸钠和所合成的Cd0.5Zn0.5S固溶体为底物,乙二醇作为溶剂和还原剂,通过一步溶剂热方法合成了NiSe/Cd0.5Zn0.5S异质结光催化剂;本发明的异质结光催化剂在可见光下的最大产氢速率达到70.3 mmol/h/g,是单纯Cd0.5Zn0.5S固溶体活性的2.35倍,且制备方法绿色环保,操作简单,活性稳定,大大提高了光催化剂对太阳光尤其是可见光的利用率,能够获得更高的经济效益。
Description
技术领域
本发明属于光催化剂制备和应用领域,具体涉及一种以NiSe为助剂构建的高效异质结光催化剂及其制备方法和应用。
背景技术
能源问题是当今国际社会关系到国计民生的重要问题之一。自从1972年Fujishima和Honda实现光电催化分解水制氢的开创性发现以来,通过太阳能驱动水分解获得最清洁的能源—氢气这一途径立刻引起了全球科学家的高度关注。CdS半导体具有合适的带隙(~2.4 eV),被认为是有希望的可见光驱使水分解的光催化剂。然而,由于光激发电子和空穴的高复合率,单纯的CdS半导体通常显示出弱的光催化产氢活性。将宽带系的ZnS和CdS结合所形成的Cd0.5Zn0.5S固溶体展现出相当好的光催化产氢活性。然而,为实现更高效地利用太阳能、提高经济效益,有必要进一步提高CdxZn1-xS固溶体的光催化活性。以Cd0.5Zn0.5S固溶体作为主催化剂来构建半导体异质结可以有效加快Cd0.5Zn0.5S固溶体中光生电荷载流子的分离和转移,从而显著增强光催化反应活性。目前,研究者们已经开发了大量的过渡金属基助催化剂来构建半导体异质结。镍,作为一种地球上含量丰富的非贵金属也已广泛应用于光催化领域,比如其氧化物,氢氧化物,硫化物,氮化物,磷化物等。但是这些材料存在光催化效率普遍不高,金属化合物的化学/物理性质不稳定等问题。因此,进一步开发和拓展新型高效的非贵金属类助催化剂材料成为光解水方向的一个重要课题。
发明内容
本发明的目的在于构建NiSe助催化剂修饰的NiSe/Cd0.5Zn0.5S异质结光催化剂,并探索其在光催化分解水产氢反应中的活性,以解决Cd0.5Zn0.5S在光催化分解水产氢中电荷载流子易复合和贵金属修饰带来的高成本问题。本发明通过一步溶剂热方法,利用乙二醇同时作溶剂和还原剂,制备出了一系列不同NiSe含量的NiSe/Cd0.5Zn0.5S异质结光催化剂。其中1%NiSe/Cd0.5Zn0.5S异质结表现出70.3 mmol/h/g的最大产氢速率,是单纯Cd0.5Zn0.5S固溶体产氢活性的2.35 倍,并且远超过多数文献报道的CdxZn1-xS基催化剂的产氢活性。本发明中的NiSe/Cd0.5Zn0.5S异质结光催化剂具有制备方法绿色环保、操作简单,可见光驱动、高产氢活性、高稳定性等优点,大大提高了光催化剂对太阳光尤其是可见光的利用率,能够获得更高的经济效益。
为实现上述目的,本发明采用如下技术方案:
一种具有可见光活性的NiSe/Cd0.5Zn0.5S高效异质结光催化剂的制备方法,包括以下步骤:
将等摩尔量的乙酸镉·二水合物和乙酸锌·二水合物加入到100 mL的反应釜内衬中,加入一定量去离子水搅拌溶解,之后在搅拌下将10 mL 4 mol/L的NaOH水溶液用吸管逐滴缓慢加入到上述溶液,搅拌30分钟后,将一定量的硫代乙酰胺加入到上述溶液。之后再次搅拌30分钟,然后将其密封于高压反应釜中,在电热鼓风干燥箱中加热到180℃,并保温24小时。待降温冷却至室温后,将沉淀离心分离、洗涤并干燥得到Cd0.5Zn0.5S固溶体。
将一定量六水合硫酸镍、亚硒酸钠按摩尔比为1:1溶解于乙二醇溶剂中,后再加入一定量所合成的Cd0.5Zn0.5S固溶体,搅拌均匀后转入高压反应釜中,180℃保持24小时,最后自然降温至室温;所得样品用去离子水和无水乙醇离心洗涤,真空烘箱烘干后得到一系列不同NiSe负载量的NiSe/Cd0.5Zn0.5S异质结光催化剂。准确称取10 mg所合成的光催化剂置于光解水反应器中进行光解水产氢性能测试。
本发明的有益效果在于:
(1)本发明将NiSe助催化剂与具有相匹配带隙的Cd0.5Zn0.5S半导体结合构建了NiSe/Cd0.5Zn0.5S异质结光催化剂,该材料的制备只需要简单的溶剂热反应,而且该方法制备过程简单、条件温和,绿色环保;
(2)NiSe助催化剂进一步提高了Cd0.5Zn0.5S半导体的光催化分解水产氢性能,最大产氢速率达到了70.3 mmol/h/g,是单纯Cd0.5Zn0.5S固溶体活性的2.35 倍,远超过多数文献报道的CdxZn1-xS基催化剂的产氢活性。
(3)匹配的带隙结构和异质结的存在加快了光生电子-空穴对的分离和转移,促进了产氢活性的提高,进一步丰富了NiSe助催化剂在光催化中的应用。
附图说明
图1中(a)为本发明中Cd0.5Zn0.5S、1%NiSe/Cd0.5Zn0.5S和10%NiSe/Cd0.5Zn0.5S的X射线衍射图谱以及六方硫化镉、立方硫化锌和六方硒化镍的标准卡片对比;(b)为本发明中Cd0.5Zn0.5S和负载不同NiSe含量的NiSe/Cd0.5Zn0.5S异质结的XRD图谱;(c)为NiSe的标准XRD图谱;
图2为本发明中Cd0.5Zn0.5S固溶体(a和b)和1%NiSe/Cd0.5Zn0.5S异质结 (c和d) 的扫描电镜图;
图3 中(a) 为Cd0.5Zn0.5S(CZS)、NiSe 和具有不同比例NiSe的NiSe/Cd0.5Zn0.5S (CZS)异质结的紫外-可见吸收光谱图;(b) 为Cd0.5Zn0.5S纳米粒子的光学带隙能值图;(c)为采用500、1000 和 1500 Hz 所测得的Cd0.5Zn0.5S固溶体的莫特-肖特基曲线图;(d) 为Cd0.5Zn0.5S和 NiSe纳米粒子的详细带隙结构图;
图4为 Cd0.5Zn0.5S固溶体 (CZS)和负载不同NiSe含量的NiSe/Cd0.5Zn0.5 (NiSe/CZS)异质结在0.35 mol/L的硫化钠和0.25 mol/L亚硫酸钠(牺牲剂)水溶液中可见光 (λ≥420nm) 照射下的光解水产氢速率比较图。
具体实施方式
本发明的制备步骤如下:
Cd0.5Zn0.5S固溶体的制备:称量10 mmol的乙酸镉·二水合物和10 mmol的乙酸锌·二水合物加入到100 mL的反应釜内衬中,加入 40 ml的去离子水搅拌溶解,之后在磁力搅拌下将10 mL 4 mol/L的NaOH水溶液用吸管逐滴加入到上述溶液,溶液逐渐变成白色粘稠糊状物,搅拌30分钟后,将25毫摩的硫代乙酰胺搅拌下加入到上述溶液。反应混合物逐渐变黄,之后再次搅拌30分钟,然后将其密封于高压反应釜中,在电热鼓风干燥箱中加热到180℃,并保温24小时。待降温冷却至室温后,将沉淀离心分离,依次用水和乙醇分别洗几次,并在真空烘箱中80℃干燥8小时,得到Cd0.5Zn0.5S固溶体。
将一定量六水合硫酸镍、亚硒酸钠按摩尔比为1:1溶解于40mL的乙二醇溶剂中,后再加入一定量Cd0.5Zn0.5S固溶体,搅拌均匀后转入高压反应釜中,180℃保持24小时,最后自然降温至室温。所得样品用去离子水和无水乙醇离心洗涤,真空烘箱中干燥后得到一系列不同NiSe负载量的NiSe/Cd0.5Zn0.5S异质结光催化剂。准确称取10 mg所合成的光催化剂置于光解水反应器中进行光解水产氢性能测试。
实施例1
将一定量六水合硫酸镍、亚硒酸钠(14.53 μmoL)按摩尔比为1:1溶解于40mL的乙二醇溶剂中,后再加入一定量Cd0.5Zn0.5S固溶体(40 mg),搅拌均匀后转入高压反应釜中,180℃保持24小时,最后自然降温至室温。所得样品用去离子水和无水乙醇离心洗涤,真空烘箱烘干后得到NiSe负载量为0.5%的NiSe/Cd0.5Zn0.5S异质结光催化剂。准确称取10 mg所合成的粉末催化剂置于光解水反应器里进行光解水产氢性能测试。
实施例2
将一定量六水合硫酸镍、亚硒酸钠(29.06 μmoL)按摩尔比为1:1溶解于40mL的乙二醇溶剂中,后再加入一定量Cd0.5Zn0.5S固溶体(40mg),搅拌均匀后转入高压反应釜中,180℃保持24小时,最后自然降温至室温。所得样品用去离子水和无水乙醇离心洗涤,真空烘箱烘干后得到NiSe负载量为1%的NiSe/Cd0.5Zn0.5S异质结光催化剂。准确称取10 mg所合成的粉末催化剂置于光解水反应器里进行光解水产氢性能测试。
实施例3
将一定量六水合硫酸镍、亚硒酸钠(58.12 μmoL)按摩尔比为1:1溶解于40mL的乙二醇溶剂中,后再加入一定量Cd0.5Zn0.5S固溶体(40mg),搅拌均匀后转入高压反应釜中,180℃保持24小时,最后自然降温至室温。所得样品用去离子水和无水乙醇离心洗涤,真空烘箱烘干后得到NiSe负载量为2%的NiSe/Cd0.5Zn0.5S异质结光催化剂。准确称取10mg所合成的粉末催化剂置于光解水反应器里进行光解水产氢性能测试。
实施例4
将一定量六水合硫酸镍、亚硒酸钠(145.29 μmoL)按摩尔比为1:1溶解于40mL的乙二醇溶剂中,后再加入一定量Cd0.5Zn0.5S固溶体(40mg),搅拌均匀后转入高压反应釜中,180℃保持24小时,最后自然降温至室温。所得样品用去离子水和无水乙醇离心洗涤,真空烘箱烘干后得到NiSe负载量为5%的NiSe/Cd0.5Zn0.5S异质结光催化剂。准确称取10 mg所合成的粉末催化剂置于光解水反应器里进行光解水产氢性能测试。
实施例5
将一定量六水合硫酸镍、亚硒酸钠(290.58 μmoL)按摩尔比为1:1溶解于40mL的乙二醇溶剂中,后再加入一定量Cd0.5Zn0.5S固溶体(40mg),搅拌均匀后转入高压反应釜中,180℃保持24小时,最后自然降温至室温。所得样品用去离子水和无水乙醇离心洗涤,真空烘箱烘干后得到NiSe负载量为10%的NiSe/Cd0.5Zn0.5S异质结光催化剂。准确称取10 mg所合成的粉末催化剂置于光解水反应器里进行光解水产氢性能测试。
性能测试
光解水产氢性能测试:取10 mg的催化剂超声分散在100 mL 0.35mol/L Na2S和0.25mol/L Na2SO3水溶液中。对反应体系先用真空泵抽至真空体系,并用循环冷凝水将反应体系的温度控制在5℃,用300W 氙灯在可见光下(λ ≥420 nm)照射反应体系,每隔1小时用气象色谱检测所得氢气量。
本发明制备得到的NiSe/Cd0.5Zn0.5S异质结光催化剂的X射线粉末衍射图如图1所示,Cd0.5Zn0.5S的XRD衍射峰与文献报道的结果相一致,显示出从六方CdS向立方ZnS转变的形式。10%NiSe/Cd0.5Zn0.5S样品中位于33.0o的衍射峰归属于NiSe (101) 面的衍射峰,表明所合成的化合物由Cd0.5Zn0.5S和NiSe两种晶相组成。图2是样品的扫描电镜图,可以观察到Cd0.5Zn0.5固溶体呈现出大小约为60 nm的均匀纳米颗粒(图2(a) 和2(b)),而在1%NiSe/Cd0.5Zn0.5S异质结样品中可以观察到较小尺寸的Cd0.5Zn0.5S固溶体均匀的分散在较大颗粒的NiSe颗粒表面(图2(c) 和2(d))。图3 (a)是样品的紫外可见漫反射谱图,可以看出Cd0.5Zn0.5S固溶体在400-500 nm之间的可见光区展现出强的吸收,其吸收边缘延伸到了约510 nm处,在500-800 nm之间随着异质结中NiSe含量的增加,吸收也逐渐增强; (b)由Tauc曲线所获得的Cd0.5Zn0.5S纳米粒子的光学带隙能,约为2.68 eV;(c)测得的Cd0.5Zn0.5S固溶体的莫特-肖特基曲线,用于测量其导带边电势;(d) Cd0.5Zn0.5S 和 NiSe纳米粒子的详细带隙结构图。 图4为负载不同NiSe含量的NiSe/Cd0.5Zn0.5S异质结光催化剂在0.35mol/LNa2S和0.25mol/L Na2SO3水溶液中的光解水产氢速率,可以看出1%NiSe/Cd0.5Zn0.5S异质结展现出最高的产氢速率。
以上所述仅为本发明的较佳实施范例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (6)
1.一种具有可见光活性的NiSe/Cd0.5Zn0.5S高效异质结光催化剂的制备方法,其特征在于:包括以下步骤:
(1)以醋酸镉、醋酸锌和硫代乙酰胺分别作为镉、锌和硫源,采用沉淀-水热法制备了Cd0.5Zn0.5S固溶体;
(2)将六水合硫酸镍和亚硒酸钠溶解于乙二醇溶剂中,然后再加入所合成的Cd0.5Zn0.5S固溶体,搅拌均匀后转入高压反应釜中进行反应,然后自然降温至室温;
(3)将步骤(2)所得产物用去离子水和无水乙醇离心洗涤,真空干燥后得到不同NiSe负载量的NiSe/Cd0.5Zn0.5S高效异质结光催化剂。
2.根据权利要求1所述的制备方法,其特征在于:步骤(2)中六水合硫酸镍和亚硒酸钠的摩尔比为1:1。
3.根据权利要求1所述的制备方法,其特征在于:步骤(2)中反应温度为180℃,时间为24h。
4.根据权利要求1所述的制备方法,其特征在于:步骤(3)所述的NiSe/Cd0.5Zn0.5S异质结光催化剂中NiSe负载量为0.5%-10%。
5.一种如权利要求1-4任一项所述的制备方法制得的具有可见光活性的NiSe/Cd0.5Zn0.5S高效异质结光催化剂。
6.一种如权利要求5所述的NiSe/Cd0.5Zn0.5S高效异质结光催化剂的应用,其特征在于:所述光催化剂在可见光下实现了高效的光催化分解水产氢活性。
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