Enhancing the Photocatalytic Hydrogen Evolution Performance of a Metal/Semiconductor Catalyst through Modulation of the Schottky Barrier Height by Controlling the Orientation of the Interface.
Construction of a metal-semiconductor heterojunction is a promising method to improve heterogeneous photocatalysis for various reactions. Although the structure and photocatalytic performance of such a catalyst system have been extensively studied, few reports have demonstrated the effect of interface orientation at the metal-semiconductor junction on junction-barrier bending and the electronic transport properties. Here, we construct a Pt/PbS heterojunction, in which Pt nanoparticles are used as highly active catalysts and PbS nanocrystals (NCs) with well-controlled shapes are used as light-harvesting supports. Experimental results show that the photoelectrocatalytic activities of the Pt/PbS catalyst are strongly dependent on the contacting facets of PbS at the junction. Pt/octahedral PbS NCs with exposed PbS(111) facets show the highest photoinduced enhancement of hydrogen evolution reaction activity, which is ∼14.38 times higher than that of the ones with only PbS(100) facets (Pt/cubic PbS NCs). This enhancement can further be rationalized by the different energy barriers of the Pt/PbS Schottky junction due to the specific band structure and electron affinity, which is also confirmed by the calculations based on density functional theory. Therefore, controlling the contacting interfaces of a metal/semiconductor material may offer an effective approach to form the desired heterojunction for optimization of the catalytic performance.
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering and ‡University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University , 800 Dongchuan Road, Shanghai 200240, P. R. China.
Yang
Y
Liu
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering and ‡University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University , 800 Dongchuan Road, Shanghai 200240, P. R. China.
Xin
X
Gu
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering and ‡University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University , 800 Dongchuan Road, Shanghai 200240, P. R. China.
Wen
W
Qi
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering and ‡University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University , 800 Dongchuan Road, Shanghai 200240, P. R. China.
Hong
H
Zhu
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering and ‡University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University , 800 Dongchuan Road, Shanghai 200240, P. R. China.
Hao
H
Shan
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering and ‡University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University , 800 Dongchuan Road, Shanghai 200240, P. R. China.
Wenlong
W
Chen
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering and ‡University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University , 800 Dongchuan Road, Shanghai 200240, P. R. China.
Peng
P
Tao
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering and ‡University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University , 800 Dongchuan Road, Shanghai 200240, P. R. China.
Chengyi
C
Song
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering and ‡University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University , 800 Dongchuan Road, Shanghai 200240, P. R. China.
Wen
W
Shang
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering and ‡University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University , 800 Dongchuan Road, Shanghai 200240, P. R. China.
Tao
T
Deng
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering and ‡University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University , 800 Dongchuan Road, Shanghai 200240, P. R. China.
Jianbo
http://orcid.org/0000-0002-3574-5585
J
Wu
Schottky junction; energy bending; hydrogen evolution reaction; interface control; photocatalysis