CN108579765A - 硫化铜/钒酸铋双层膜复合材料的制备及作为光电阳极的应用 - Google Patents
硫化铜/钒酸铋双层膜复合材料的制备及作为光电阳极的应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title abstract description 101
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 91
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 10
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- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 7
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052697 platinum Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
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- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 3
- 229910052700 potassium Inorganic materials 0.000 claims 3
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- 239000007864 aqueous solution Substances 0.000 claims 2
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- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 238000011109 contamination Methods 0.000 claims 1
- 150000002085 enols Chemical class 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
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- 125000001292 4,6-dihydroxy-1,3-phenylene group Chemical group OC1=C(C=C(C(=C1)O)*)* 0.000 description 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种硫化铜/钒酸铋双层膜复合材料的制备方法,是先用电化学沉积法制备出多孔BiVO4光电极,再用简单的滴涂方式将CuS负载于BiVO4电极上,得到CuS/BiVO4双层膜复合材料。由于CuS是一种窄带隙p‑型半导体,禁带宽度几乎接近半导体Si材料,具有较好的可见光吸收性能及导电性;BiVO4是一种具有高可见光响应性、电子结构可调的n‑型半导体,二者复合形成双层CuS/BiVO4薄膜,构成价带和导带相交错的p‑n异质结构,这种结构有助于光生载流子的快速分离,减小电子‑空穴对复合,从而提高了BiVO4的光电化学性能,使其作为光电阳极材料在光催化分解水产氢反应中具有很好的应用前景。
Description
技术领域
本发明涉及一种BiVO4基复合材料,尤其涉及一种CuS/BiVO4双层膜复合材料的制备方法,主要作为光电阳极材料应用于光催化分解水产氢反应中。
背景技术
由于地球上可利用资源有限,再加上近几年来人类过度消耗能源,造成能源短缺的严重现象。因此,开发新能源是全人类亟待需要解决的问题。太阳能是一种取之不尽,用之不竭的可再生能源,通过各种方法将其转化为电能、氢能等多种形式能量储存。氢能被认为是理想的清洁能源,因其燃烧值比较高,且产物无污染,被广泛的用于代替化石燃料来解决能源短缺和环境污染问题。许多学者致力于这一问题的解决,光催化分解水技术和光电解水技术应运而生。目前,窄带隙半导体结合太阳光组成光电化学池是取得清洁能源的一种既环保又简便的有效方法之一,相比于传统的ZnO、TiO2等宽带隙半导体,BiVO4因其具有高可见光响应性,电子结构可调,无毒等优点被深入研究并视为新型光电阳极材料。但是,以BiVO4作为光电催化剂在光电化学反应过程中,其光生载流子的复合依然较为严重,导致光电流密度低,光稳定性较差。因此,减小BiVO4光阳极的光生电子-空穴对复合是有效提高其光电化学性能的关键。
在众多改性方法中,宽带隙半导体与窄带隙半导体耦合构成能带匹配的促进光生电子和空穴分离的理想体系是常见的一种方法。金属硫化物作为空穴牺牲剂通常被用以与较宽带隙半导体复合形成简单的双层复合薄膜结构。例如,有文献报道Bi2S3与BiVO4,WO3等耦合能有效提高本体催化剂的光电化学性能。然而过渡金属硫化物(CuS)也是一种物理化学性能优良的催化剂,被作为光催化降解有机污染物催化剂,光催化制氢催化剂,超级电容器电极材料,锂离子电池中阳极等,但是其作为催化剂作为光电阳极材料的应用上未见报道。
发明内容
本发明的目的是提供一种CuS/BiVO4双层膜复合材料的制备方法,主要用于光催化制氢反应中。
一、CuS/BiVO4复合材料的制备
本发明CuS/BiVO4复合材料的制备,是先用电化学沉积法制备出多孔BiVO4光电极,再用简单的滴涂方式将CuS负载于BiVO4电极上,得到CuS/BiVO4薄膜。具体工艺如下:
(1)电解液的配制:将碘化钾(KI)磁力搅拌溶解于蒸馏水中,得到浓度0.06~0.07g/mL的碘化钾溶液,用硝酸(HNO3)调节溶液pH至1.5~1.6;再将五水硝酸铋(Bi(NO3)3•5H2O)加入碘化钾溶液中,剧烈搅拌直至完全溶解,得到橙红色混合溶液;然后将对苯醌的乙醇溶液缓慢滴加入上述橙红色混合溶液中,搅拌10~15min,即得电化学沉积制备BiOI纳米片薄膜的电解液;碘化钾与五水硝酸铋的质量比为1:0.28~1:0.30;碘化钾与对苯醌的质量比为1:0.14~1:0.16。
(2)BiOI薄膜的制备:以铂片作对电极,Ag/AgCl电极作参比电极,FTO导电玻璃作工作电极,以上述制备电解液中进行电沉积:电沉积条件:电位窗口为0V~-0.13V,扫速为5mV/s,扫描圈数是10圈;电沉积完成后,用二次蒸馏水冲洗,并在60~80℃下干燥,得BiOI薄膜。
(3)BiVO4薄膜的制备:将乙酰丙酮氧钒(VO(acac)2)搅拌溶解于二甲基亚砜(DMSO)中得到乙酰丙酮氧钒溶液;再用微量注射器汲取乙酰丙酮氧钒溶液,均匀滴涂于步骤(2)获得的BiOI薄膜上;然后置于用马弗炉中,在400~450℃下煅烧2~2.5h;待温度降至室温,将粗产品取出,于0.1~1M NaOH溶液中浸泡30~120min,取出,在60~80℃下干燥,即得黄色BiVO4薄膜。
(4)花状CuS的制备:将二水氯化铜(CuCl2·2H2O)溶解在蒸馏水中形成CuCl2·2H2O溶液;将硫脲溶解在无水乙醇中得到硫脲溶液;再将两种溶液混合(溶液混合中二水氯化铜(CuCl2·2H2O)与硫脲的质量比为1:0.88~1:0.90)后剧烈搅拌20~30 min得悬浮液;然后将悬浮液于100~150℃下水热反应10~12 h;反应完成后,自然冷却至室温,得到墨绿色的沉淀物;离心,用二次蒸馏水、无水乙醇洗涤,干燥,研磨成粉末,即得花状CuS。
(5)CuS/BiVO4薄膜的制备:将上述制备的花状CuS粉体分散于聚乙烯醇(PVA)的二次蒸馏水溶液中,超声30~60 min,得到CuS与聚乙烯醇的悬浮液;再将悬浮液通过滴涂方式包覆在上述制备的BiVO4薄膜表面,然后于100~150 ℃下煅烧2~2.5 h,自然冷却至室温,即得CuS/BiVO4双层膜复合材料。
上述悬浮液中,聚乙烯醇(PVA)的含量为0.004~0.005g/mL;花状CuS粉体与聚乙烯醇(PVA)的质量比为1:1.004~1:0.996。CuS与聚乙烯醇的悬浮液包覆在BiVO4薄膜表面的量为0.4~0.6ul/mm2。所得CuS/BiVO4双层膜复合材料中,CuS的负载量为22~33%。
二、CuS/BiVO4复合材料的表征
图1 为上述制备的花状CuS、多孔BiVO4薄膜、CuS/BiVO4双层膜的XRD图谱。分析图1可知,BiVO4薄膜是纯净单斜晶系的结构,与标准卡片(JCPDS. No. 14-0688)吻合。其余在26°,42°,53°,62°,65°的衍射峰是来自于FTO玻璃中的SnO2。除了这些,没有检测到任何其他杂质峰,表明已经成功获得了纯净的单斜晶系BiVO4。当花状CuS层涂于BiVO4表面,新的衍射峰出现,在50°左右衍射峰处刚好有对应CuS粉体强衍射峰,且BiVO4主要的衍射峰并没有因为CuS层的覆盖而被削弱。这是由于在27.9°处,CuS也有较弱的峰。CuS的XRD谱图与已报道的康乃馨状CuS一致,在2θ=27.9°,29.5°,31.4°,48.1°和59.0°分别对应斜方晶系CuS的(111),(112),(023),(130)和(223)晶面。XRD图谱分析表明,CuS/BiVO4复合薄膜已成功制备。
图2为上述制备的BiVO4、CuS及CuS/BiVO4的SEM图。可以清晰地看到,CuS是由纳米片组装成一朵朵康乃馨状小花,滴涂于多孔BiVO4膜表面后,看到CuS纳米花均匀分散在BiVO4表面(a,b)。为了使CuS纳米小花与BiVO4膜紧密接触,将其放于马弗炉中,在较低温度(150℃)下煅烧2 h。图(c、d)是煅烧后的CuS/BiVO4复合薄膜的扫描电镜图。可见,煅烧过的薄膜的形貌并没有太大的改变,但花状CuS花瓣稍有塌陷,绽放的花朵有收缩的趋势。在测试光电化学解水产氢性能时发现,不管是在纯Na2SO4溶液中,还是在Na2S-Na2SO3牺牲剂混合体系中,CuS/BiVO4都避免不了光腐蚀带来的不利影响。因此,在表面再涂了一层TiO2薄膜,如图(e、f)看图发现,团聚的TiO2颗粒在CuS表面。
综上所述,本发明利用简单的滴涂法将一定浓度花状CuS聚乙烯醇悬浊液包覆于多孔BiVO4纳米膜上,大大提升了纯的BiVO4对可见光的吸收强度。CuS是一种窄带隙p-型半导体,禁带宽度几乎接近半导体Si材料,且在紫外到近红外光区都有强吸收,花状CuS具有较好的可见光吸收性能,还有良好导电性。BiVO4是一种具有高可见光响应性、电子结构可调的n-型半导体,二者复合形成双层CuS/BiVO4薄膜,具有p-n异质结结构。CuS/BiVO4构成价带和导带相交错的p-n异质结构,这种结构有助于光生载流子的快速分离,减小电子-空穴对复合,从而提高了BiVO4的光电化学性能,使其作为光电阳极材料在光催化分解水产氢反应中具有很好的应用前景。
附图说明
图1 为本发明制备的花状CuS、多孔BiVO4薄膜、CuS/BiVO4双层膜的XRD图谱。
图2 为本发明制备的花状CuS、多孔BiVO4薄膜、CuS/BiVO4双层膜的的SEM图。
图3为BiVO4、CuS/BiVO4、CuS薄膜样品的紫外可见漫反射光谱图(A)和光子能量与(αhν)2的斜率表示的禁带宽度值(B)。
图4为 BiVO4、CuS/BiVO4和CuS薄膜材料的光电流-电压曲线图:(A) 暗反应;(B)可见光下。0.5 M Na2SO4作为电解液,扫速50 mV/s。
图5为BiVO4、CuS/BiVO4薄膜样品在不同偏压下的时间-电流曲线图:(A) 0.1 V,(B) 0.3 V,(C) 0.6 V。
图6为BiVO4和CuS/BiVO4薄膜在不同条件下的奈奎斯曲线:(A)暗反应下;(B)可见光下。
图7 为BiVO4和CuS/BiVO4薄膜的在加了牺牲剂之后的电压-电流图:(A)暗反应下;(B)可见光照下;(C)在0.6 V偏压下,BiVO4和CuS/BiVO4薄膜的时间-电流图。
图8为 BiVO4薄膜系列样品的电压-电流曲线图。
图9 为BiVO4、CuS/BiVO4和CuS薄膜的模特-肖特基势垒曲线。
具体实施方式
下面通过具体实施例对本发明CuS/BiVO4双层膜的制备、性能及应用作进一步说明。
一、CuS/BiVO4双层膜的制备
(1)花状CuS的制备
将2.046 g二水氯化铜(CuCl2·2H2O)、1.827 g 硫脲分别溶解在28 ml二次蒸馏水和14 ml无水乙醇混合液中。然后将CuCl2·2H2O溶液缓慢滴加入硫脲溶液中,待溶液全部滴加完毕,此时的悬浮液需在室温下再剧烈搅拌30 min。将上述搅拌后的反应液转入100 ml聚四氟乙烯内衬中,140 ℃加热12 h,反应完成后,自然冷却至室温,得到墨绿色的沉淀物。将所得沉淀物离心,分别用二次蒸馏水、无水乙醇洗涤数次,60 ℃下干燥6 h,研磨成粉末。
(2)BiOI薄膜的制备
a、电解液的制备:将3.32 g碘化钾(KI)溶解于50 ml二次蒸馏水中,用1 M硝酸(HNO3)调节上述溶液pH值约为1.5。称取0.970 g五水硝酸铋(Bi(NO3)3·5H2O)加入上述溶液中,且剧烈搅拌直至完全溶解,溶液颜色逐渐由黑红色变为橙红色。称取0.498g对苯醌(C6H4O2),加入到20 ml无水乙醇中,搅拌溶解得到棕色的苯醌乙醇溶液,并将对苯醌乙醇溶液缓慢滴加入到上述橙红色混合液中,滴加完毕后再搅拌10~15min,即得电解液;
b、BiOI薄膜的制备:在三电极体系中利用循环伏安法电沉积制备BiOI薄膜。三电极分别为:铂片作对电极,Ag/AgCl电极作参比电极,FTO导电玻璃作工作电极(使用前用异丙醇、丙酮、无水乙醇、二次蒸馏水依次超声清洗)。电沉积条件:电位窗口为0V~-0.13V,扫速为5mV/s,扫描圈数是10圈,电沉积都在室温下进行。电沉积完成后,用二次蒸馏水冲洗并在60℃下干燥。
(3)BiVO4电极的制备
取0.133 g乙酰丙酮氧钒(C10H14O5V)加入到2.5 ml 二甲基亚砜(DMSO)中,搅拌至溶解。用微量注射器取100 μL上述溶液均匀滴于BiOI薄膜上。再用马弗炉在450 ℃下煅烧2h,得粗产品取出。最后将BiVO4/FTO电极浸入0.1 M NaOH溶液中30~120min,取出,在60 ℃下干燥,得到黄色的BiVO4薄膜。
(4)CuS/BiVO4薄膜的制备
称取0.05 g的CuS粉体分散于10 ml含有0.05 g聚乙烯醇(PVA)的二次蒸馏水中,超声60 min,得到比较粘稠的悬浮液。移取上述悬浮液200 μL滴涂在BiVO4表面(滴涂量为0.4~0.6ul/mm2),再在150℃下煅烧2 h,自然冷却至室温后,取出,即得CuS/BiVO4双层膜复合材料。
二、CuS/BiVO4双层膜的光电性能测试
图3是BiVO4薄膜系列样品的紫外可见漫反射光谱及禁带宽度计算评估图。其中图3(A)为BiVO4、CuS/BiVO4、CuS薄膜样品的紫外可见漫反射光谱图。图3(B)为BiVO4、CuS/BiVO4、CuS薄膜样品的光子能量与(αhν)2的斜率表示的禁带宽度值。如图3(A)所示,BiVO4薄膜吸收边缘在500 nm左右,与以报道文献基本一致。且禁带宽度计算值大约为2.48 eV。表明了BiVO4在可见光下光吸收性能。当在表面涂了花状CuS以后,BiVO4对光的吸收明显增强,且拓宽了光的吸收范围,吸收边缘达到556 nm左右。禁带宽度减小到2.42eV。单一的CuS吸光范围很宽,其禁带宽度大概在1.6~1.8 eV之间,然而吸收强度比复合薄膜材料弱,这是由于CuS膜很薄的缘故。表征结果表明,CuS的加入不仅拓宽了BiVO4对可见光的吸收,而且形成p-n异质结,有利于光生载流子的有效分离,降低光生电子-空穴对的复合。
图4为 BiVO4、CuS/BiVO4和CuS薄膜材料的光电流-电压曲线图:(A)暗反应;(B)可见光下。0.5 M Na2SO4作为电解液,扫速50 mV/s。从图中可以明显看到,CuS是一种性能优异的电催化剂,其导电性能良好。在电势大于0V范围内,在纯Na2SO4电解液中发生电化学反应,可获得较大电流密度。在暗反应下,几乎没有检测到其电流密度,说明它在暗处反应时非常稳定。在可见照下,虽然增加了其光电流密度,但远小于复合薄膜CuS/BiVO4的光电流密度。表明,CuS层包覆于BiVO4薄膜表面,可以削弱BiVO4光生载流子复合几率,增强对可见光的吸收,产生更多激发光子,提高载流子的密度。因此,CuS/BiVO4复合薄膜获得较高的光电流密度。
图5为BiVO4、CuS/BiVO4薄膜样品在不同偏压下的时间-电流曲线图:(A)0.1 V;(B)0.3 V;(C)0.6 V。由图5可知,不管是在哪个偏压下,CuS/BiVO4膜的光电流密度都高于纯的BiVO4膜。但是复合薄膜材料的光稳定性能较差,这是由金属硫化物光腐蚀引起的。
图6为BiVO4和CuS/BiVO4薄膜在不同条件下的奈奎斯曲线:(A)暗反应下;(B)可见光下。结合图6可知,光照条件下更有利于光生载流子在催化剂表面及电解液界面传输,CuS的引入也促进了光生电子-空穴对的分离。这个结果很好地对应了以上LSV的分析。
为了消除CuS光腐蚀带来的严重危害,改用NaS2-Na2SO3混合液体系作为电解液,测试纯的BiVO4薄膜及复合物CuS/BiVO4薄膜的光电化学性能,如图7所示。通过比较发现,复合材料在正电压区仍然体现较好的光电化学性能,但光腐蚀现象依然较为严重。
为了减小CuS光腐蚀的影响,将TiO2层再涂于CuS/BiVO4复合膜上,以起到对CuS的保护作用,如图8所示。由图可知,直接将单一TiO2颗粒包覆于BiVO4表面并不能提高本体BiVO4的光电流密度。但在正电压区,TiO2/CuS/BiVO4复合薄膜材料的电流密度都要高于纯的BiVO4。结果证明了CuS才是提高BiVO4光电化学性能的因素,TiO2在本实验中只起到了对CuS膜的保护作用。因此,通过本实验研究可以发现,光稳定性也是光电化学反应需要重点考虑的方面,对于一些不稳定或光腐蚀较为明显的催化剂,可以选择其他一些较为稳定的材料作为保护层,实现光电阳极兼具理想的光电性能和光稳定性的效果。
图9为 BiVO4、CuS/BiVO4和CuS薄膜的模特-肖特基势垒曲线。分析图9,BiVO4样品曲线线性部分做切线得到直线斜率为正,BiVO4是一种典型的n-型半导体。在表面包覆一层花状CuS后,其斜率增大,表明光电子越容易分离,光电化学性能越好。然而,图中展示的纯的CuS薄膜的肖特基势垒曲线,做切线所得直线斜率为负,CuS属于p-型半导体。结果表明CuS/BiVO4复合薄膜可构成p-n结结构,有利于电子-空穴对的快速分离。
Claims (8)
1.一种CuS/BiVO4复合材料的制备方法,包括以下步骤:
(1)电解液的配制:将碘化钾磁力搅拌溶解于蒸馏水中,得到浓度0.06~0.07g/mL的碘化钾溶液,并用硝酸调节溶液pH至1.5~1.6;再将五水硝酸铋加入碘化钾溶液中,剧烈搅拌直至完全溶解,得到橙红色混合溶液;然后将对苯醌的乙醇溶液缓慢滴加入上述橙红色混合溶液中,搅拌10~15min,即得电化学沉积制备BiOI纳米片薄膜的电解液;
(2)BiOI薄膜的制备:以铂片作对电极,Ag/AgCl电极作参比电极,FTO导电玻璃作工作电极,以上述制备电解液中进行电沉积;电沉积条件:电位窗口为0V~-0.13V,扫速为5mV/s,扫描圈数是10圈;电沉积完成后,用二次蒸馏水冲洗,并在60~80℃下干燥,得到BiOI薄膜;
(3)BiVO4薄膜的制备:将乙酰丙酮氧钒搅拌溶解至二甲基亚砜中得到乙酰丙酮氧钒溶液;再用微量注射器汲取乙酰丙酮氧钒溶液,均匀滴涂于步骤(2)获得的BiOI薄膜上;然后置于用马弗炉中,在400~450℃下煅烧2~2.5h;待温度降至室温,将粗产品取出,于0.1~1 MNaOH溶液中浸泡30~120min,取出,在60~80℃下干燥,即得黄色BiVO4薄膜;
(4)花状CuS的制备:将二水氯化铜溶解在蒸馏水中形成CuCl2·2H2O溶液;将硫脲溶解在无水乙醇中得到硫脲溶液;再将两种溶液混合后剧烈搅拌20~30 min得悬浮液;然后将悬浮液于100~150℃下水热反应10~12 h;反应完成后,自然冷却至室温,得到墨绿色的沉淀物;离心,用二次蒸馏水、无水乙醇洗涤,干燥,研磨成粉末,即得花状CuS;
(5)CuS/BiVO4薄膜的制备:将花状CuS粉体分散于聚乙烯醇的二次蒸馏水溶液中,超声30~60min,得到CuS与聚乙烯醇的悬浮液;再将悬浮液通过滴涂方式包覆在上述制备的BiVO4薄膜表面,然后在100~150 ℃下煅烧2~2.5 h,自然冷却至室温,即得CuS/BiVO4复合材料。
2.如权利要求1所述一种CuS/BiVO4复合材料的制备方法,其特征在于:步骤(1)中,碘化钾与五水硝酸铋的质量比为1:0.28~1:0.30。
3.如权利要求1所述一种CuS/BiVO4复合材料的制备方法,其特征在于:步骤(1)中,碘化钾与对苯醌的质量比为1:0.14~1:0.16。
4.如权利要求1所述一种CuS/BiVO4复合材料的制备方法,其特征在于:步骤(4)中,二水氯化铜与硫脲的质量比为1:0.88~1:0.90。
5.如权利要求1所述一种CuS/BiVO4复合材料的制备方法,其特征在于:步骤(5)中,聚乙烯醇的二次蒸馏水溶液中,聚乙烯醇的含量为0.004~0.005g/mL。
6.如权利要求1所述一种CuS/BiVO4复合材料的制备方法,其特征在于:步骤(5)中,花状CuS粉体与聚乙烯醇的质量比为1:1.004~1:0.996。
7.如权利要求1所述一种CuS/BiVO4复合材料的制备方法,其特征在于:步骤(5)中,CuS与聚乙烯醇的悬浮液包覆在BiVO4薄膜表面的量为0.4~0.6ul/mm2。
8.如权利要求1所述方法制备的CuS/BiVO4复合材料作为光电阳极应用于光催化分解水产氢反应中。
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