Chen Xi, Zheng Xuchen, Qi Lu, Xue Yurui, Li Yuliang
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P.R. China.
University of Chinese Academy of Sciences, Beijing 100049, P.R. China.
ACS Mater Au. 2022 Apr 2;2(3):321-329. doi: 10.1021/acsmaterialsau.1c00071. eCollection 2022 May 11.
Sp-C-hybridized alkyne bonds present the natural advantages of interacting with metal atoms and have the ability to generate a large number of new catalytic active sites on the surface and the interfaces, thus greatly promoting the efficient progress of various light/electrochemical reactions. In this work, we have successfully fabricated a novel type of interfacial structure containing sp-C-Mo/O bonds and mixed Mo valence states with outstanding catalytic activity and stability for photoelectrocatalytic (PEC) overall water splitting in a wide pH range (0-14), due to the presence of sp-carbon-rich graphdiyne. For example, in alkaline conditions (pH = 14), the overpotentials of oxygen and hydrogen evolution reactions at 10 mA cm are 165 and 8 mV. When being used as an electrolyzer, the cell voltage of this catalyst is only 1.40 V to achieve 10 mA cm. The high PEC activity of graphdiyne@molybdenum oxide originates from the conversion of chemical bonds at the sp-C hybrid interface and the coexistence of multivalent states of molybdenum, triggering a large number of catalytic active sites, greatly promoting charge transfer and lowering water dissociation energy.
sp-C杂化炔键具有与金属原子相互作用的天然优势，并且能够在表面和界面上产生大量新的催化活性位点，从而极大地促进各种光/电化学反应的高效进行。在这项工作中，由于存在富含sp-碳的石墨炔，我们成功制备了一种新型的包含sp-C-Mo/O键和混合钼价态的界面结构，该结构在宽pH范围（0-14）内对光电催化（PEC）全水分解具有出色的催化活性和稳定性。例如，在碱性条件（pH = 14）下，10 mA cm时析氧反应和析氢反应的过电位分别为165和8 mV。当用作电解槽时，该催化剂的电池电压仅为1.40 V即可达到10 mA cm。石墨炔@氧化钼的高PEC活性源于sp-C杂化界面处化学键的转变以及钼多价态的共存，引发了大量催化活性位点，极大地促进了电荷转移并降低了水的解离能。
