Matched micro-geometrical configuration leading to hetero-interfacial intimate contact of MoS2@UiO-66-NH2 Z-scheme heterojunction for efficient photocatalytic CO2 reduction
Matched micro-geometrical configuration leading to hetero-interfacial intimate contact of MoS2@UiO-66-NH2 Z-scheme heterojunction for efficient photocatalytic CO2 reduction
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DOI：
10.1016/j.jmst.2023.10.021
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发表时间：
2023-11
期刊：
影响因子：
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通讯作者：
Xin Yang;Tianyu Wang;Huiyang Ma;Weiliang Shi;Zhengqiang Xia;Qi Yang;Pan Zhang;Ren Ma;Gang Xie;Sanping Chen
中科院分区：
文献类型：
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作者：
Xin Yang;Tianyu Wang;Huiyang Ma;Weiliang Shi;Zhengqiang Xia;Qi Yang;Pan Zhang;Ren Ma;Gang Xie;Sanping Chen
当异质界面紧密接触是高性能Z-方案异质结结构的中心时，Z-方案异质结是一种有效的光催化策略。本文将具有广泛光吸收、高电导率、稳定的UIO-66-NH_2(Y)(y=100,300,500 nm)和富Lewis酸中心的x-MoS_2[x=平板(P)，花(F)，固体球(S)]集成到一系列X-MoS_2@UIO-66-NH_2(Y)Z-晶型异质结中，对其进行了充分表征，并将其用于光催化CO_2(PCO_2RR)生成CH4和CO。针对MoS2难以改性和复合材料接触松散的问题，对UIO-66-NH_2的微观几何构型和MoS_2的形貌进行了优化，以实现紧密接触。具有完全匹配的微观几何构型的Z型异质结f-MoS_2@UIO-66-NH_2(100 Nm)表现出良好的电子消耗速率(REE)为263.78μμ·g~(-1)·h~(-1)，CH4产率为27.18 mol·g~(-1)·h~(-1)，选择性为82.44%，远远优于大多数基于MoS_2和MOF的异质结。通过大量的光电表征、控制实验和密度泛函理论计算表明，f-MoS_2@UIO-66-NH_2(100 Nm)的优异光催化性能归因于：(I)UIO-66-NH_2的小尺寸增强了相互取向，增加了外表面，最大限度地增加了与MoS_2的异质界面接触，加速了界面电荷转移；(Ii)具有最佳基面曲率的f-MoS_2的分级结构大大减少了接触势垒，呈现出高电荷吞吐量，电荷激发率为1.967 mV，顺利地启动了8电子CO2甲烷化反应。此外，还研究了f-MoS_2@UIO-66-NH_2(100 Nm)的耐久性能。
Z-scheme heterojunction is an effective strategy in photocatalysis, when hetero-interfacial intimate contact is the center of high-performance Z-scheme heterojunction structure. Here,x-MoS2[x= plate (p), flower (f), and solid sphere (s)] with extensive optical absorption and high conductivity and stable UiO-66-NH2(y) (y= 100, 300, and 500 nm) with rich Lewis's acid sites were integrated to a series ofx-MoS2@UiO-66-NH2(y) Z-scheme heterojunctions, which were fully characterized and used for photocatalytic reduction of CO2(pCO2RR) into CH4and CO. In response to the difficult modification of MoS2and loose contact of composite bulk materials, the micro-geometric configurations on the size of UiO-66-NH2and the morphology of MoS2were optimized to achieve an intimate contact. The Z-scheme heterojunction f-MoS2@UiO-66-NH2(100 nm) with perfectly matched micro-geometric configuration exhibited an excellent electron consumption rate (Rele) of 263.78 μmol g–1h–1and a high CH4yield of 27.18 μmol g–1h–1with a selectivity of 82.44%, being far superior to most MoS2- and MOFs-based heterojunctions. Comprehensive investigations with extensive photoelectric characterizations, control experiments, and density functional theory (DFT) calculations demonstrate that the excellent photocatalytic performance of f-MoS2@UiO-66-NH2(100 nm) could be attributed to that (i) the low size of UiO-66-NH2strengthens mutual alignment and increases outer surface to maximize heterointerface contact with MoS2, accelerating the interfacial charge transfer; (ii) the hierarchical structure of f-MoS2with optimal basal plane curvature greatly reduces contact barriers to present a high charge throughput with a charge excitation rate of 1.967 mV, smooth initiating the 8-electron CO2methanation. Additionally, the durability of f-MoS2@UiO-66-NH2(100 nm) was also investigated.