Fabrication of Heterogeneous-Phase Solid-Solution Promoting Band Structure and Charge Separation for Enhancing Photocatalytic CO2 Reduction: A Case of ZnXCa1-XIn2S4.
Fabrication of Heterogeneous-Phase Solid-Solution Promoting Band Structure and Charge Separation for Enhancing Photocatalytic CO2 Reduction: A Case of ZnXCa1-XIn2S4.
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DOI：
10.1021/acsami.7b08767
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发表时间：
2017-08
影响因子：
9.5
通讯作者：
Chao Zeng;Hongwei Huang;Tierui Zhang;F. Dong;Yihe Zhang;Yingmo Hu
中科院分区：
文献类型：
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作者：
Chao Zeng;Hongwei Huang;Tierui Zhang;F. Dong;Yihe Zhang;Yingmo Hu
光催化将CO2还原为太阳能燃料，为同时解决能源和环境问题展示了巨大的魅力。半导体的光还原能力与其导带（CB）位置密切相关。具有相同晶体系统的非晶相固溶体总是具有单调变化的CB位置，并且必须牺牲高CB水平以实现良性光吸收。在此，我们报告的异质相固溶体ZnXCa 1-XIn 2S 4之间的三角ZnIn 2S 4和立方CaIn 2S 4的制造。ZnXCa_（1-x）In_2S_4固溶体在540 ~ 640 nm范围内具有有序调谐的光响应，呈现出更负的CB能级和更高的电荷分离效率。得益于这些优点，所有这些ZnXCa 1-XIn 2S 4固溶体在可见光（λ > 420 nm）照射下均表现出显著增强的光催化CO2还原性能。Zn0.4Ca0.6In2S4具有最负的CB位置和最高的电荷分离效率，具有最佳的光催化CH 4和CO生成速率，分别是ZnIn 2S 4的16.7和6.8倍，CaIn 2S 4的7.2和3.9倍。为了验证非均相固溶体在提高能带结构和光催化性能方面的关键作用，合成了另一种非均相固溶体ZnXCd 1-XIn 2 S4。它还显示了一个上移的CB水平和促进电荷分离。该研究为开发高效的可见光催化剂用于CO2还原和其他光还原反应提供了新的视角。
Photocatalytic CO2 reduction into solar fuels illustrates huge charm for simultaneously settling energy and environmental issues. The photoreduction ability of a semiconductor is closely correlated to its conduction band (CB) position. A homogeneous-phase solid-solution with the same crystal system always has a monotonously changed CB position, and the high CB level has to be sacrificed to achieve a benign photoabsorption. Herein, we report the fabrication of heterogeneous-phase solid-solution ZnXCa1-XIn2S4 between trigonal ZnIn2S4 and cubic CaIn2S4. The ZnXCa1-XIn2S4 solid solutions with orderly tuned photoresponsive range from 540 to 640 nm present a more negative CB level and highly enhanced charge-separation efficiency. Profiting from these merits, all of these ZnXCa1-XIn2S4 solid solutions exhibit remarkably strengthened photocatalytic CO2 reduction performance under visible light (λ > 420 nm) irradiation. Zn0.4Ca0.6In2S4, bearing the most negative CB position and highest charge-separation efficiency, casts the optimal photocatalytic CH4 and CO evolution rates, which reach 16.7 and 6.8 times higher than that of ZnIn2S4 and 7.2 and 3.9 times higher than that of CaIn2S4, respectively. To verify the crucial role of the heterogeneous-phase solid solution in promoting the band structure and photocatalytic performance, another heterogeneous-phase solid-solution ZnXCd1-XIn2S4 has been synthesized. It also displays an upshifted CB level and promoted charge separation. This work may provide a new perspective into the development of an efficient visible-light driven photocatalyst for CO2 reduction and other photoreduction reactions.