Zhen-Yu Wu1, Mohammadreza Karamad2, Xue Yong3, Qizheng Huang1, David A Cullen4, Peng Zhu1, Chuan Xia1, Qunfeng Xiao5, Mohsen Shakouri5, Feng-Yang Chen1, Jung Yoon Timothy Kim1, Yang Xia1, Kimberly Heck1, Yongfeng Hu5, Michael S Wong1, Qilin Li6, Ian Gates2, Samira Siahrostami7, Haotian Wang8,9,10,11. 1. Department of Chemical and Biomolecular Engineering, Rice University, Houston, TX, USA. 2. Department of Chemical and Petroleum Engineering, University of Calgary, Calgary, AB, Canada. 3. Department of Chemistry, University of Calgary, Calgary, AB, Canada. 4. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, USA. 5. Canadian Light Source Inc., University of Saskatchewan, Saskatoon, SK, Canada. 6. Department of Civil and Environmental Engineering, Rice University, Houston, TX, USA. 7. Department of Chemistry, University of Calgary, Calgary, AB, Canada. samira.siahrostami@ucalgary.ca. 8. Department of Chemical and Biomolecular Engineering, Rice University, Houston, TX, USA. htwang@rice.edu. 9. Department of Materials Science and NanoEngineering, Rice University, Houston, TX, USA. htwang@rice.edu. 10. Department of Chemistry, Rice University, Houston, TX, USA. htwang@rice.edu. 11. Azrieli Global Scholar, Canadian Institute for Advanced Research (CIFAR), Toronto, ON, Canada. htwang@rice.edu.
Abstract
Electrochemically converting nitrate, a widespread water pollutant, back to valuable ammonia is a green and delocalized route for ammonia synthesis, and can be an appealing and supplementary alternative to the Haber-Bosch process. However, as there are other nitrate reduction pathways present, selectively guiding the reaction pathway towards ammonia is currently challenged by the lack of efficient catalysts. Here we report a selective and active nitrate reduction to ammonia on Fe single atom catalyst, with a maximal ammonia Faradaic efficiency of ~ 75% and a yield rate of up to ~ 20,000 μg h-1 mgcat.-1 (0.46 mmol h-1 cm-2). Our Fe single atom catalyst can effectively prevent the N-N coupling step required for N2 due to the lack of neighboring metal sites, promoting ammonia product selectivity. Density functional theory calculations reveal the reaction mechanisms and the potential limiting steps for nitrate reduction on atomically dispersed Fe sites.
Electrochemically converting n class="Chemical">nitrate, a widespread water pollutant, back to valuable ammonia is a green and delocalized route for ammonia synthesis, and can be an appealing and supplementary alternative to the Haber-Bosch process. However, as there are other nitrate reduction pathways present, selectively guiding the reaction pathway towards ammonia is currently challenged by the lack of efficient catalysts. Here we report a selective and active nitrate reduction to ammonia on Fesingle atom catalyst, with a maximal ammonia Faradaic efficiency of ~ 75% and a yield rate of up to ~ 20,000 μg h-1 mgcat.-1 (0.46 mmol h-1 cm-2). Our Fesingle atom catalyst can effectively prevent the N-Ncoupling step required for N2 due to the lack of neighboring metalsites, promoting ammonia product selectivity. Density functional theory calculations reveal the reaction mechanisms and the potential limiting steps for nitrate reduction on atomically dispersed Fesites.
Authors: K Honkala; A Hellman; I N Remediakis; A Logadottir; A Carlsson; S Dahl; C H Christensen; J K Nørskov Journal: Science Date: 2005-01-28 Impact factor: 47.728
Authors: Yang Song; Daniel Johnson; Rui Peng; Dale K Hensley; Peter V Bonnesen; Liangbo Liang; Jingsong Huang; Fengchang Yang; Fei Zhang; Rui Qiao; Arthur P Baddorf; Timothy J Tschaplinski; Nancy L Engle; Marta C Hatzell; Zili Wu; David A Cullen; Harry M Meyer; Bobby G Sumpter; Adam J Rondinone Journal: Sci Adv Date: 2018-04-27 Impact factor: 14.136
Authors: Wenhui He; Jian Zhang; Stefan Dieckhöfer; Swapnil Varhade; Ann Cathrin Brix; Anna Lielpetere; Sabine Seisel; João R C Junqueira; Wolfgang Schuhmann Journal: Nat Commun Date: 2022-03-02 Impact factor: 17.694