Operando NMR spectroscopic analysis of proton transfer in heterogeneous photocatalytic reactions.
Proton transfer (PT) processes in solid-liquid phases play central roles throughout chemistry, biology and materials science. Identification of PT routes deep into the realistic catalytic process is experimentally challenging, thus leaving a gap in our understanding. Here we demonstrate an approach using operando nuclear magnetic resonance (NMR) spectroscopy that allows to quantitatively describe the complex species dynamics of generated H2/HD gases and liquid intermediates in pmol resolution during photocatalytic hydrogen evolution reaction (HER). In this system, the effective protons for HER are mainly from H2O, and CH3OH evidently serves as an outstanding sacrificial agent reacting with holes, further supported by our density functional theory calculations. This results rule out controversy about the complicated proton sources for HER. The operando NMR method provides a direct molecular-level insight with the methodology offering exciting possibilities for the quantitative studies of mechanisms of proton-involved catalytic reactions in solid-liquid phases.
Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China.
Xue Lu
XL
Wang
Department of Physics, Shanghai Key Laboratory of Magnetic Resonance, East China Normal University, Shanghai 200062, China.
Wenqing
W
Liu
Key Laboratory for Advanced Materials, Centre for Computational Chemistry, Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, China.
Yan-Yan
YY
Yu
Department of Physics, Shanghai Key Laboratory of Magnetic Resonance, East China Normal University, Shanghai 200062, China.
Yanhong
Y
Song
Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China.
Wen Qi
WQ
Fang
Department of Physics, Shanghai Key Laboratory of Magnetic Resonance, East China Normal University, Shanghai 200062, China.
Daxiu
D
Wei
Key Laboratory for Advanced Materials, Centre for Computational Chemistry, Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, China.
Xue-Qing
XQ
Gong
Department of Physics, Shanghai Key Laboratory of Magnetic Resonance, East China Normal University, Shanghai 200062, China.|NYU-ECNU Institute of Physics at NYU Shanghai, 3663 Zhongshan Road North, Shanghai 200062, China.
Ye-Feng
YF
Yao
Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China.
Hua Gui
HG
Yang