Inert basal plane activation of two-dimensional ZnIn2S4viaNi atom doping for enhanced co-catalyst free photocatalytic hydrogen evolution
Inert basal plane activation of two-dimensional ZnIn2S4viaNi atom doping for enhanced co-catalyst free photocatalytic hydrogen evolution
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通过 Ni 原子掺杂对二维 ZnIn2S4 进行惰性基面活化，增强无助催化剂光催化析氢
DOI：
10.1039/d0ta03992f
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发表时间：
2020-07-14
影响因子：
11.9
通讯作者：
Zheng, Huajun
中科院分区：
文献类型：
--
作者：
Shi, Xiaowei;Mao, Liang;Zheng, Huajun
为了摆脱对助催化剂的依赖，设计具有合适的析氢反应本征活性中心和有效分离载流子的光催化剂是关键。在本论文中，我们首次在二维六方结构的ZnIn2S4(ZIS)Viani原子掺杂(Ni-ZIS)中激发了惰性基面S原子的催化活性。密度泛函理论计算(DFT)和X射线吸收精细结构(XAFS)研究表明，Ni原子较好地取代了ZIS中的Zn原子。而引入Ni原子将在费米能级附近形成新的杂化态，并调制邻近S原子的电子性质，从而优化氢吸附自由能，增强她的动力学。另外，FS-瞬变吸收光谱测量表明，Ni-ZIS中的光激电子具有较长的恢复寿命。结果表明，Ni-ZIS具有较高的光催化活性，在可见光(波长420 nm)照射下的析氢速率为4220 mU·mol·g~(-1)·h~(-1)，约为ZIS的3.2倍。在380和420 nm处的表观量子效率分别高达19.7%和17.1%。这种单原子调制策略为在没有共催化剂的情况下提高ZIS对HER的光催化活性提供了一条简单而有前景的途径。
Designing photocatalysts with appropriate intrinsic active sites for the hydrogen evolution reaction (HER) and efficient charge-carrier separation is critical to get rid of the dependence on co-catalysts. Herein, we for the first time trigger the catalytic activity of inert basal plane S atoms in two-dimensional hexagonal ZnIn2S4(ZIS)viaNi atom doping (Ni-ZIS). Density functional theory calculations (DFT) and X-ray absorption fine structure (XAFS) investigations reveal that Ni atoms preferably replace Zn atoms in ZIS. And introducing Ni atoms would form new hybridized states near the Fermi level and modulate the electronic properties of their neighboring S atoms, leading to optimized hydrogen adsorption free energy and enhanced HER kinetics. Additionally, fs-transient absorption spectroscopy measurements illustrate a prolonged recovery lifetime of photoexcited electrons in Ni-ZIS. Consequently, Ni-ZIS exhibits an improved photocatalytic activity with a hydrogen evolution rate of 4220 mu mol g(-1)h(-1)under visible light irradiation (lambda> 420 nm) without any co-catalysts, roughly 3.2 times higher than that of ZIS. The apparent quantum efficiency at 380 and 420 nm could reach as high as 19.7% and 17.1%, respectively. This single atom modulation strategy presents a facile and promising pathway to enhance the photocatalytic activity of ZIS for the HER without co-catalysts.