Stable and Efficient Single-Atom Zn Catalyst for CO2 Reduction to CH4
- Lili HanLili HanCenter for Electron Microscopy and Tianjin Key Lab of Advanced Functional Porous Materials, Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, ChinaDepartment of Physics and Astronomy, University of California, Irvine, California 92697, United StatesMore by Lili Han,
- Shoujie SongShoujie SongCenter for Electron Microscopy and Tianjin Key Lab of Advanced Functional Porous Materials, Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, ChinaMore by Shoujie Song,
- Mingjie LiuMingjie LiuCenter for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United StatesMore by Mingjie Liu,
- Siyu YaoSiyu YaoChemistry Division, Brookhaven National Laboratory, Upton, New York 11973, United StatesMore by Siyu Yao,
- Zhixiu LiangZhixiu LiangChemistry Division, Brookhaven National Laboratory, Upton, New York 11973, United StatesMore by Zhixiu Liang,
- Hao ChengHao ChengDepartment of Physics and Astronomy, University of California, Irvine, California 92697, United StatesMore by Hao Cheng,
- Zhouhong RenZhouhong RenCenter for Electron Microscopy and Tianjin Key Lab of Advanced Functional Porous Materials, Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, ChinaMore by Zhouhong Ren,
- Wei LiuWei LiuCenter for Electron Microscopy and Tianjin Key Lab of Advanced Functional Porous Materials, Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, ChinaMore by Wei Liu,
- Ruoqian LinRuoqian LinChemistry Division, Brookhaven National Laboratory, Upton, New York 11973, United StatesMore by Ruoqian Lin,
- Gaocan QiGaocan QiSchool of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, ChinaMore by Gaocan Qi,
- Xijun Liu*Xijun Liu*[email protected]Center for Electron Microscopy and Tianjin Key Lab of Advanced Functional Porous Materials, Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, ChinaMore by Xijun Liu,
- Qin Wu*Qin Wu*[email protected]Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United StatesMore by Qin Wu,
- Jun Luo*Jun Luo*[email protected]Center for Electron Microscopy and Tianjin Key Lab of Advanced Functional Porous Materials, Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, ChinaMore by Jun Luo, and
- Huolin L. Xin*Huolin L. Xin*[email protected]Department of Physics and Astronomy, University of California, Irvine, California 92697, United StatesMore by Huolin L. Xin
Abstract

The development of highly active and durable catalysts for electrochemical reduction of CO2 (ERC) to CH4 in aqueous media is an efficient and environmentally friendly solution to address global problems in energy and sustainability. In this work, an electrocatalyst consisting of single Zn atoms supported on microporous N-doped carbon was designed to enable multielectron transfer for catalyzing ERC to CH4 in 1 M KHCO3 solution. This catalyst exhibits a high Faradaic efficiency (FE) of 85%, a partial current density of −31.8 mA cm–2 at a potential of −1.8 V versus saturated calomel electrode, and remarkable stability, with neither an obvious current drop nor large FE fluctuation observed during 35 h of ERC, indicating a far superior performance than that of dominant Cu-based catalysts for ERC to CH4. Theoretical calculations reveal that single Zn atoms largely block CO generation and instead facilitate the production of CH4.
Cited By
This article is cited by 31 publications.
- Dunfeng Gao, Tianfu Liu, Guoxiong Wang, Xinhe Bao. Structure Sensitivity in Single-Atom Catalysis toward CO2 Electroreduction. ACS Energy Letters 2021, 6 (2) , 713-727. https://doi.org/10.1021/acsenergylett.0c02665
- Lili Han, Machuan Hou, Pengfei Ou, Hao Cheng, Zhouhong Ren, Zhixiu Liang, J. Anibal Boscoboinik, Adrian Hunt, Iradwikanari Waluyo, Shusheng Zhang, Longchao Zhuo, Jun Song, Xijun Liu, Jun Luo, Huolin L. Xin. Local Modulation of Single-Atomic Mn Sites for Enhanced Ambient Ammonia Electrosynthesis. ACS Catalysis 2021, 11 (2) , 509-516. https://doi.org/10.1021/acscatal.0c04102
- Md Estak Ahmed, Suzanne Adam, Dibyajyoti Saha, Jennifer Fize, Vincent Artero, Abhishek Dey, Carole Duboc. Repurposing a Bio-Inspired NiFe Hydrogenase Model for CO2 Reduction with Selective Production of Methane as the Unique C-Based Product. ACS Energy Letters 2020, 5 (12) , 3837-3842. https://doi.org/10.1021/acsenergylett.0c02002
- Wenyao Chen, Weizhong Zheng, Junbo Cao, Wenzhao Fu, Gang Qian, De Chen, Xinggui Zhou, Xuezhi Duan. Atomic Insights into Robust Pt–PdO Interfacial Site-Boosted Hydrogen Generation. ACS Catalysis 2020, 10 (19) , 11417-11429. https://doi.org/10.1021/acscatal.0c03214
- Yan Liu, Guoxing Zhu, Ang Li, Jiajing Pei, Yamin Zheng, Wenxing Chen, Jun Ding, Wenjie Wu, Tao Wang, Dingsheng Wang, Junjie Mao. Transforming cobalt hydroxide nanowires into single atom site catalysts. Nano Energy 2021, 83 , 105799. https://doi.org/10.1016/j.nanoen.2021.105799
- Xuewan Wang, Jinmeng Sun, Tingting Li, Zhongxin Song, Dan Wu, Bin Zhao, Kun Xiang, Wei Ai, Xian-Zhu Fu, Jing-Li Luo. Folic acid self-assembly synthesis of ultrathin N-doped carbon nanosheets with single-atom metal catalysts. Energy Storage Materials 2021, 36 , 409-416. https://doi.org/10.1016/j.ensm.2021.01.024
- Shenglin Yan, Samah A. Mahyoub, Juhua Zhong, Chengzhen Chen, Fanghua Zhang, Zhenmin Cheng. Ultrathin and dense Ag nanosheets synthesis under suppressed face (111) growth and surface diffusion. Journal of Power Sources 2021, 488 , 229484. https://doi.org/10.1016/j.jpowsour.2021.229484
- Li Xu, Daijie Deng, Yuhui Tian, Hongping Li, Junchao Qian, Jianchun Wu, Henan Li. Dual-active-sites design of CoNx anchored on zinc-coordinated nitrogen-codoped porous carbon with efficient oxygen catalysis for high-stable rechargeable zinc-air batteries. Chemical Engineering Journal 2021, 408 , 127321. https://doi.org/10.1016/j.cej.2020.127321
- Jiguang Zhang, Yuting Guo, Bin Shang, Tingting Fan, Xinyi Lian, Pingping Huang, Yunyun Dong, Zhou Chen, Xiaodong Yi. Unveiling the Synergistic Effect between Graphitic Carbon Nitride and Cu 2 O toward CO 2 Electroreduction to C 2 H 4. ChemSusChem 2021, 14 (3) , 929-937. https://doi.org/10.1002/cssc.202002427
- Madeleine K. Wilsey, Connor P. Cox, Ryland C. Forsythe, Luke R. McCarney, Astrid M. Müller. Selective CO 2 reduction towards a single upgraded product: a minireview on multi-elemental copper-free electrocatalysts. Catalysis Science & Technology 2021, 11 (2) , 416-424. https://doi.org/10.1039/D0CY02010A
- Qiyou Wang, Chao Cai, Minyang Dai, Junwei Fu, Xiaodong Zhang, Huangjingwei Li, Hang Zhang, Kejun Chen, Yiyang Lin, Hongmei Li, Junhua Hu, Masahiro Miyauchi, Min Liu. Recent Advances in Strategies for Improving the Performance of CO 2 Reduction Reaction on Single Atom Catalysts. Small Science 2021, 1 (2) , 2000028. https://doi.org/10.1002/smsc.202000028
- Sanshuang Gao, Yifan Liu, Zhongyuan Xie, Yuan Qiu, Longchao Zhuo, Yongji Qin, Junqiang Ren, Shusheng Zhang, Guangzhi Hu, Jun Luo, Xijun Liu. Metal‐Free Bifunctional Ordered Mesoporous Carbon for Reversible Zn‐CO 2 Batteries. Small Methods 2021, 52 , 2001039. https://doi.org/10.1002/smtd.202001039
- Yuanzhi Zhu, Xiaoxuan Yang, Cheng Peng, Cameron Priest, Yi Mei, Gang Wu. Carbon‐Supported Single Metal Site Catalysts for Electrochemical CO 2 Reduction to CO and Beyond. Small 2021, 364 , 2005148. https://doi.org/10.1002/smll.202005148
- Runbo Zhao, Peng Ding, Peipei Wei, Longcheng Zhang, Qian Liu, Yonglan Luo, Tingshuai Li, Siyu Lu, Xifeng Shi, Shuyan Gao, Abdullah M. Asiri, Zhiming Wang, Xuping Sun. Recent Progress in Electrocatalytic Methanation of CO 2 at Ambient Conditions. Advanced Functional Materials 2021, 10 , 2009449. https://doi.org/10.1002/adfm.202009449
- Jiangbo Xi, Hyun Seung Jung, Yun Xu, Fei Xiao, Jong Wook Bae, Shuai Wang. Synthesis Strategies, Catalytic Applications, and Performance Regulation of Single‐Atom Catalysts. Advanced Functional Materials 2021, 130 , 2008318. https://doi.org/10.1002/adfm.202008318
- Lili Han, Zhouhong Ren, Pengfei Ou, Hao Cheng, Ning Rui, Lili Lin, Xijun Liu, Longchao Zhuo, Jun Song, Jiaqiang Sun, Jun Luo, Huolin L. Xin. Modulating Single‐Atom Palladium Sites with Copper for Enhanced Ambient Ammonia Electrosynthesis. Angewandte Chemie 2021, 133 (1) , 349-354. https://doi.org/10.1002/ange.202010159
- Lili Han, Zhouhong Ren, Pengfei Ou, Hao Cheng, Ning Rui, Lili Lin, Xijun Liu, Longchao Zhuo, Jun Song, Jiaqiang Sun, Jun Luo, Huolin L. Xin. Modulating Single‐Atom Palladium Sites with Copper for Enhanced Ambient Ammonia Electrosynthesis. Angewandte Chemie International Edition 2021, 60 (1) , 345-350. https://doi.org/10.1002/anie.202010159
- Changhyeok Choi, Sungho Yoon, Yousung Jung. Shifting the scaling relations of single-atom catalysts for facile methane activation by tuning the coordination number. Chemical Science 2021, 285 https://doi.org/10.1039/D0SC05632D
- Chaochen Xu, Anthony Vasileff, Yao Zheng, Shi‐Zhang Qiao. Recent Progress of 3d Transition Metal Single‐Atom Catalysts for Electrochemical CO 2 Reduction. Advanced Materials Interfaces 2020, 7 , 2001904. https://doi.org/10.1002/admi.202001904
- Hyeonuk Choi, Dong-Kyu Lee, Mi-Kyung Han, Gnanaprakasam Janani, Subramani Surendran, Jin Hyeok Kim, Jung Kyu Kim, Hoonsung Cho, Uk Sim. Review—Non-Noble Metal-Based Single-Atom Catalysts for Efficient Electrochemical CO 2 Reduction Reaction. Journal of The Electrochemical Society 2020, 167 (16) , 164503. https://doi.org/10.1149/1945-7111/abc593
- Zijun Yue, Caixia Ou, Nengwen Ding, Lihong Tao, Jianjun Zhao, Jun Chen. Advances in Metal Phthalocyanine based Carbon Composites for Electrocatalytic CO 2 Reduction. ChemCatChem 2020, 12 (24) , 6103-6130. https://doi.org/10.1002/cctc.202001126
- Yuchao Wang, Yi Liu, Wei Liu, Jiao Wu, Qian Li, Qingguo Feng, Zhiyan Chen, Xiang Xiong, Dingsheng Wang, Yongpeng Lei. Regulating the coordination structure of metal single atoms for efficient electrocatalytic CO 2 reduction. Energy & Environmental Science 2020, 13 (12) , 4609-4624. https://doi.org/10.1039/D0EE02833A
- Defeng Qi, Yifan Liu, Min Hu, Xianyun Peng, Yuan Qiu, Shusheng Zhang, Wei Liu, Hongyi Li, Guangzhi Hu, Longchao Zhuo, Yongji Qin, Jia He, Gaocan Qi, Jiaqiang Sun, Jun Luo, Xijun Liu. Engineering Atomic Sites via Adjacent Dual‐Metal Sub‐Nanoclusters for Efficient Oxygen Reduction Reaction and Zn‐Air Battery. Small 2020, 16 (48) , 2004855. https://doi.org/10.1002/smll.202004855
- Huiwang Dai, Wenjun Zhou, Wei Wang. Co/N co-doped carbonaceous polyhedron as efficient peroxymonosulfate activator for degradation of organic pollutants: Role of cobalt. Chemical Engineering Journal 2020, , 127921. https://doi.org/10.1016/j.cej.2020.127921
- Li Lu, Xianjun Cao, Ziyan Shen, Lu Li, Juanjuan Huo, Weihua Chen, Chuntai Liu, Hao Liu. Electrospun nitrogen-doped carbon nanofibers for electrocatalysis. Sustainable Materials and Technologies 2020, 26 , e00221. https://doi.org/10.1016/j.susmat.2020.e00221
- Yuhang Li, Aoni Xu, Yanwei Lum, Xue Wang, Sung-Fu Hung, Bin Chen, Ziyun Wang, Yi Xu, Fengwang Li, Jehad Abed, Jianan Erick Huang, Armin Sedighian Rasouli, Joshua Wicks, Laxmi Kishore Sagar, Tao Peng, Alexander H. Ip, David Sinton, Hao Jiang, Chunzhong Li, Edward H. Sargent. Promoting CO2 methanation via ligand-stabilized metal oxide clusters as hydrogen-donating motifs. Nature Communications 2020, 11 (1) https://doi.org/10.1038/s41467-020-20004-7
- Huishan Shang, Zhenghang Zhao, Jiajing Pei, Zhuoli Jiang, Danni Zhou, Ang Li, Juncai Dong, Pengfei An, Lirong Zheng, Wenxing Chen. Dynamic evolution of isolated Ru–FeP atomic interface sites for promoting the electrochemical hydrogen evolution reaction. Journal of Materials Chemistry A 2020, 8 (43) , 22607-22612. https://doi.org/10.1039/D0TA08940K
- Jie Xu, Shuhua Lai, Defeng Qi, Min Hu, Xianyun Peng, Yifan Liu, Wei Liu, Guangzhi Hu, Heng Xu, Fan Li, Chao Li, Jia He, Longchao Zhuo, Jiaqiang Sun, Yuan Qiu, Shusheng Zhang, Jun Luo, Xijun Liu. Atomic Fe-Zn dual-metal sites for high-efficiency pH-universal oxygen reduction catalysis. Nano Research 2020, 1 https://doi.org/10.1007/s12274-020-3186-x
- Yong Zheng, Hui Song, Shan Chen, Xiaohui Yu, Jixin Zhu, Jingsan Xu, Kai A. I. Zhang, Chao Zhang, Tianxi Liu. Metal‐Free Multi‐Heteroatom‐Doped Carbon Bifunctional Electrocatalysts Derived from a Covalent Triazine Polymer. Small 2020, 16 (47) , 2004342. https://doi.org/10.1002/smll.202004342
- Zhao Hu, Xiaofang Li, Sushu Zhang, Qin Li, Jiajie Fan, Xianlin Qu, Kangle Lv. Fe 1 /TiO 2 Hollow Microspheres: Fe and Ti Dual Active Sites Boosting the Photocatalytic Oxidation of NO. Small 2020, 16 (47) , 2004583. https://doi.org/10.1002/smll.202004583
- Jian Wang, Juwon Kim, Subin Choi, Hongsheng Wang, Jongwoo Lim. A Review of Carbon‐Supported Nonprecious Metals as Energy‐Related Electrocatalysts. Small Methods 2020, 4 (10) , 2000621. https://doi.org/10.1002/smtd.202000621




