Multi-touch cobalt phosphide-tungsten phosphide heterojunctions anchored on reduced graphene oxide boosting wide pH hydrogen evolution  

具有多触点界面的CoP-WP/rGO异质结助力宽pH析氢

作　　者：Yanqing Jiao Haijing Yan Dongxu Wang Xiuwen Wang Siwei Xu Ying Xie Aiping Wu Li Jiang Chungui Tian Ruihong Wang Honggang Fu 焦艳清;闫海静;王东旭;王秀文;许思薇;谢颖;吴爱平;姜莉;田春贵;王瑞红;付宏刚(Key Laboratory of Functional Inorganic Material Chemistry,Ministry of Education,Heilongjiang University,Harbin 150080,China;Heilongjiang Provincial Key Laboratory of Surface Active Agent and Auxiliary,Qiqihar University,Qiqihar 161006,China)

机构地区：[1]Key Laboratory of Functional Inorganic Material Chemistry,Ministry of Education,Heilongjiang University,Harbin 150080,China [2]Heilongjiang Provincial Key Laboratory of Surface Active Agent and Auxiliary,Qiqihar University,Qiqihar 161006,China

出　　处：《Science China Materials》2022年第5期1225-1236,共12页中国科学（材料科学（英文版）

基　　金：financially supported by the National Key R&D Program of China (2018YFB1502401);the National Natural Science Foundation of China (91961111, 22171074, 21601055, U20A20250, 21805073, and 22005161);the Natural Science Foundation of Heilongjiang Province (ZD2021B003);China Postdoctoral Science Foundation (2017M611406);the Postdoctoral Science Foundation of Heilongjiang Province (LBH-Z16175);the Scientific Research Funds of University Affiliated to Heilongjiang Province (KJCX201913)。

摘　　要：Multi-interface engineering is deemed as an effective strategy to boost catalytic activity via electronic structure modulation. However, it is still a big challenge due to the phase-separation tendency. Herein, we designed CoP-WP heterojunctions with multi-touch interfaces using Co_(8)W_(18), a definite structure polyoxometalate-based polynuclear cobalt molecular cluster, as a precursor. The Co P-WP heterojunctions anchored on reduced graphene oxide(Co P-WP/r GO)were obtained by growing Co_(8)W_(18)on GO followed by phosphorization. The intrinsic {Co-O-W} coordination modes in Co_(8)W_(18)are conducive to the formation of the multiple interfaces between CoP and WP. The abundant intimate interfaces in Co P-WP heterojunctions promote the electron transfer from WP to Co P, thus regulating the interfacial electronic structure and optimizing the hydrogen adsorption free energy(ΔGH*), as verified by X-ray photoelectron spectroscopy analysis and theoretical calculations. Furthermore, the integration of r GO provides Co P-WP/r GO with a large surface area and high conductivity, aiding mass transport and charge transfer. Co P-WP/r GO exhibits remarkable hydrogen evolution reaction(HER) activity with low overpotentials of 96, 130,and 138 m V at 10 m A cm^(-2)in alkaline, acidic and neutral media, respectively, and has long-term durability. Our discovery provides an opportunity to design heterojunction materials with multi-coupled interfaces at low-cost and efficient HER catalysts.界面工程是一种通过调整电子结构提高催化活性的有效手段.然而,构建具有紧密接触界面的异质结仍然面临巨大的挑战.本研究工作中,我们引入具有确定结构的多酸基多核钴分子团簇Co_(8)W_(18)作为前驱体,构建了紧密接触的多重界面耦合的Co P-WP异质结.通过在氧化石墨烯上生长Co_(8)W_(18),磷化处理后获得了锚定在还原氧化石墨烯上的Co P-WP异质结(Co P-WP/r GO). Co_(8)W_(18)中固有的{Co-O-W}配位模式有利于形成紧密接触的界面. X射线光电子能谱分析和理论计算证实了Co P-WP异质结中丰富的紧密接触界面促进了电子从WP向Co P的转移,从而调节了界面电子结构,优化了氢吸附自由能(ΔGH*).与氧化石墨的复合使得Co P-WP/r GO具有大的表面积和高的电导性,有利于物质传输和电荷转移.因此, Co P-WP/r GO在碱性、酸性和中性介质中皆表现出显著增强的HER活性,在10 m A cm^(-2)下过电位分别为96、130和138 m V.这项工作为设计具有多触点界面的异质结材料用作低成本和高效HER电催化剂提供了一种新策略.

关 键 词：HETEROJUNCTION modulating electronic structure electrocatalytic hydrogen evolution metal phosphides poly-oxometalates 

分 类 号：TQ116.2[化学工程—无机化工] TQ426