ZnGa(2-x)In(x)S4 (0 ≤ x ≤ 0.4) and Zn(1-2y)(CuGa)(y)Ga(1.7)In(0.3)S4 (0.1 ≤ y ≤ 0.2): optimize visible light photocatalytic H2 evolution by fine modulation of band structures.
ZnGa(2-x)In(x)S4 (0 ≤ x ≤ 0.4) and Zn(1-2y)(CuGa)(y)Ga(1.7)In(0.3)S4 (0.1 ≤ y ≤ 0.2): optimize visible light photocatalytic H2 evolution by fine modulation of band structures.
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DOI：
10.1021/ic503101s
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发表时间：
2015-02
影响因子：
4.6
通讯作者：
Jia Yang;Hao Fu;Dingfeng Yang;Wenliang Gao;Rihong Cong;Tao Yang
中科院分区：
文献类型：
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作者：
Jia Yang;Hao Fu;Dingfeng Yang;Wenliang Gao;Rihong Cong;Tao Yang
能带结构工程是开发半导体光催化剂的一种有效技术，通常是通过等价或价离子取代来实现的。从紫外光活化催化剂ZnGa2S4开始，通过In（3+）到Ga（3+）和(Cu（+)/Ga(3+)）到zn（2+）的取代，成功地开发出了良好的可见光催化剂。首先，通过降低导带位置，ZnGa2-xInxS4（0≤x≤0.4）的带隙从3.36 eV减小到3.04 eV；其次，Zn1-2y(CuGa)yGa1.7In0.3S4 （y = 0.1, 0.15, 0.2）通过提高价带最大值，几乎没有失去水还原的过电位，使光子吸收进一步显著红移到~ 500 nm。以S（2-）和SO3（2-）为牺牲试剂，Zn0.7Cu0.15Ga1.85In0.3S4在纯可见光照射下H2的析出速率最高（无贵金属样品为386 μmol/h/g，负载0.5 wt % Ru的样品为629 μmol/h/g），而采用相同方法合成的双主ZnGa2S4和ZnIn2S4分别为0和27.9 μmol/h/g。在500 nm处，Zn0.6Cu0.2Ga1.9In0.3S4（负载0.5 wt % Ru）的表观量子产率达到了7.9%。
Band structure engineering is an efficient technique to develop desired semiconductor photocatalysts, which was usually carried out through isovalent or aliovalent ionic substitutions. Starting from a UV-activated catalyst ZnGa2S4, we successfully exploited good visible light photocatalysts for H2 evolution by In(3+)-to-Ga(3+) and (Cu(+)/Ga(3+))-to-Zn(2+) substitutions. First, the bandgap of ZnGa2-xInxS4 (0 ≤ x ≤ 0.4) decreased from 3.36 to 3.04 eV by lowering the conduction band position. Second, Zn1-2y(CuGa)yGa1.7In0.3S4 (y = 0.1, 0.15, 0.2) provided a further and significant red-shift of the photon absorption to ∼500 nm by raising the valence band maximum and barely losing the overpotential to water reduction. Zn0.7Cu0.15Ga1.85In0.3S4 possessed the highest H2 evolution rate under pure visible light irradiation using S(2-) and SO3(2-) as sacrificial reagents (386 μmol/h/g for the noble-metal-free sample and 629 μmol/h/g for the one loaded with 0.5 wt % Ru), while the binary hosts ZnGa2S4 and ZnIn2S4 (synthesized using the same procedure) show 0 and 27.9 μmol/h/g, respectively. The optimal apparent quantum yield reached to 7.9% at 500 nm by tuning the composition to Zn0.6Cu0.2Ga1.9In0.3S4 (loaded with 0.5 wt % Ru).