Vacancy-defect modulated pathway of photoreduction of CO2 on single atomically thin AgInP2S6 sheets into olefiant gas
Authors: Zhenxiang Cheng
Zhigang Zou
Jinlan Wang
Shi Li
Yong Zhou
Xiaoyong Wang
Huichao He
Xiaoning Li
Yujie Xiong
Yong Yang
Qing Shen
Wa Gao
Journal: Nature Communications (2021)
Discipline: Multidisciplinary
Keywords: Artificial photosynthesis; CO2 conversion; hydrocarbon fuels; AgInP2S6; sulfur defect engineering
Affiliations: Key Laboratory of Modern Acoustics (MOE), Institute of Acoustics, School of Physics, Jiangsu Key Laboratory of Nanotechnology, Eco-materials and Renewable Energy Research Center (ERERC), National Laboratory of Solid State Microstructures, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, China., School of Physics, Southeast University, Nanjing, China., State Key Laboratory of Environmental Friendly Energy Materials, Southwest University of Science and Technology, Mianyang, China., Institute of Superconducting & Electronic Materials, Innovation Campus, University of Wollongong, Squires Way, North Wollongong, NSW, Australia., Key Laboratory of Soft Chemistry and Functional Materials (MOE), Nanjing University of Science and Technology, Nanjing, China., School of Physics, Southeast University, Nanjing, China. ., University of Electrocommunication, Grad Sch Informatics and Engineering, Chofu, Tokyo, Japan., Hefei National Laboratory for Physical Sciences at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui, China. ., Key Laboratory of Modern Acoustics (MOE), Institute of Acoustics, School of Physics, Jiangsu Key Laboratory of Nanotechnology, Eco-materials and Renewable Energy Research Center (ERERC), National Laboratory of Solid State Microstructures, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, China. .

Abstract:  Artificial photosynthesis, light-driving CO2 conversion into hydrocarbon fuels, is a promising strategy to synchronously overcome global warming and energy-supply issues. The quaternary AgInP2S6 atomic layer with the thickness of ~ 0.70 nm were successfully synthesized through facile ultrasonic exfoliation of the corresponding bulk crystal. The sulfur defect engineering on this atomic layer through a H2O2 etching treatment can excitingly change the CO2 photoreduction reaction pathway to steer dominant generation of ethene with the yield-based selectivity reaching ~73% and the electron-based selectivity as high as ~89%. Both DFT calculation and in-situ FTIR spectra demonstrate that as the introduction of S vacancies in AgInP2S6 causes the charge accumulation on the Ag atoms near the S vacancies, the exposed Ag sites can thus effectively capture the forming *CO molecules. It makes the catalyst surface enrich with key reaction intermediates to lower the C-C binding coupling barrier, which facilitates the production of ethene. 

Retracted: No

PubPeer comments:
 1. The blurring TEM image shown in supplementary Figure 7 can really confirm that no morphology changes? ![file] 2. Also, the EDS intensity of the selected area for determining the exact elemental ratio based on the bad STEM mode in supplementary Figure 8 is not convincible. ![file] 3. For the UV-vis absorption spectra shown in supplementary Figure 11, we noise level for the three line at UV region is quite similar in a, but the noise level in b after same conversion is totally different, how to explain it? ![file] ,