Defective crystalline molybdenum phosphides as bifunctional catalysts for hydrogen evolution and hydrazine oxidation reactions during water splitting

被引:33
作者
Gao, Yan [1 ]
Wang, Qiang [2 ]
He, Ting [3 ]
Zhang, Jun-Ye [3 ]
Sun, Hao [1 ]
Zhao, Bin [1 ]
Xia, Bao Yu [3 ]
Yan, Ya [1 ]
Chen, Yuan [4 ]
机构
[1] Univ Shanghai Sci & Technol, Sch Mat Sci & Engn, 516 Jungong Rd, Shanghai 200093, Peoples R China
[2] Nanjing Tech Univ, Sch Chem & Mol Engn, Dept Appl Chem, Nanjing 211880, Jiangsu, Peoples R China
[3] HUST, Sch Chem & Chem Engn, Wuhan Natl Lab Optoelect, 1037 Luoyu Rd, Wuhan 430074, Hubei, Peoples R China
[4] Univ Sydney, Sch Chem & Biomol Engn, Sydney, NSW 2006, Australia
基金
澳大利亚研究理事会; 中国国家自然科学基金;
关键词
DOPED MESOPOROUS CARBONS; EFFICIENT ELECTROCATALYST; NITROGEN; OXYGEN; NANOPARTICLES; PHOSPHOSULFIDE; GENERATION; ELECTRODES; GRAPHENE; HYBRID;
D O I
10.1039/c9qi01005j
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Molybdenum phosphides (MoP) are emerging as an attractive catalyst for water splitting due to their excellent activity and stability. However, most of the MoP synthesized so far are crystalline MoP with relatively fewer exposed active sites and low electrical conductivity. Here, we use a metallo-organic Mo precursor (MoO2(acac)(2)) to create defect-rich crystalline MoP nanoparticles and uniformly anchor them on reduced graphene oxide (denoted as D-MoP/rGO). High-temperature thermal decomposition of the precursor generates gases, which induce a variety of defects in D-MoP/rGO along with a P-rich surface composition. The electrochemically active surface area of D-MoP/rGO is 8 times that of bulk MoP. D-MoP/rGO requires a small overpotential of 122 mV for the hydrogen evolution reaction (HER) to reach a current density of 10 mA cm(-2). Furthermore, density functional theory (DFT) calculation results reveal that surface P sites are the key active sites, which favor the adsorption of H atoms and also act as an H deliverer to promote the HER. Importantly, D-MoP/rGO is also a highly active catalyst for the hydrazine oxidation reaction (HzOR) and requires a low overpotential of 84 mV to reach a current density of 10 mA cm(-2). Thus, efficient HER||HzOR hybrid water-splitting can be realized using D-MoP/rGO, which can deliver a current density of 100 mA cm(-2) at a small cell voltage of 0.74 V and undergo a stable 12 h operation. In summary, a simple method has been demonstrated to generate high-performance metal phosphide electrocatalysts for total water splitting. Furthermore, the material design concept of creating defective crystalline nanoparticles using gas generating metal precursors can serve as a general approach to create various catalytic active defective crystalline materials.
引用
收藏
页码:2686 / 2695
页数:10
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