Identification and elimination of false positives in electrochemical nitrogen reduction studies

被引:363
作者
Choi, Jaecheol [1 ,2 ]
Suryanto, Bryan H. R. [1 ]
Wang, Dabin [1 ]
Du, Hoang-Long [1 ,2 ]
Hodgetts, Rebecca Y. [1 ,2 ]
Vallana, Federico M. Ferrero [1 ]
MacFarlane, Douglas R. [1 ,2 ]
Simonov, Alexandr N. [1 ,2 ]
机构
[1] Monash Univ, Sch Chem, Clayton, Vic 3800, Australia
[2] Monash Univ, Sch Chem, ARC Ctr Excellence Electromat Sci, Clayton, Vic 3800, Australia
基金
澳大利亚研究理事会;
关键词
ELECTROCATALYTIC AMMONIA-SYNTHESIS; DINITROGEN REDUCTION; NITRATE; CATALYSTS; NITRITE; NOX; N-2; ELECTROREDUCTION; QUANTIFICATION; CONTAMINATION;
D O I
10.1038/s41467-020-19130-z
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Ammonia is of emerging interest as a liquefied, renewable-energy-sourced energy carrier for global use in the future. Electrochemical reduction of N-2 (NRR) is widely recognised as an alternative to the traditional Haber-Bosch production process for ammonia. However, though the challenges of NRR experiments have become better understood, the reported rates are often too low to be convincing that reduction of the highly unreactive N-2 molecule has actually been achieved. This perspective critically reassesses a wide range of the NRR reports, describes experimental case studies of potential origins of false-positives, and presents an updated, simplified experimental protocol dealing with the recently emerging issues. Discovering a sustainable route to ammonia as a fertiliser and as an energy carrier is critically important, but many recent reports on the electrochemical nitrogen reduction are false positives. Here the authors uncover the emerging experimental traps and detail protocols to reliably avoid them.
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页数:10
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共 57 条
[1]   Electrochemical synthesis of ammonia via Mars-van Krevelen mechanism on the (111) facets of group III-VII transition metal mononitrides [J].
Abghoui, Younes ;
Skulason, Egill .
CATALYSIS TODAY, 2017, 286 :78-84
[2]   Electroreduction of N2 to Ammonia at Ambient Conditions on Mononitrides of Zr, Nb, Cr, and V: A DFT Guide for Experiments [J].
Abghoui, Younes ;
Garden, Anna L. ;
Howat, Jakob G. ;
Vegge, Tejs ;
Skulason, Egill .
ACS CATALYSIS, 2016, 6 (02) :635-646
[3]   A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements [J].
Andersen, Suzanne Z. ;
Colic, Viktor ;
Yang, Sungeun ;
Schwalbe, Jay A. ;
Nielander, Adam C. ;
McEnaney, Joshua M. ;
Enemark-Rasmussen, Kasper ;
Baker, Jon G. ;
Singh, Aayush R. ;
Rohr, Brian A. ;
Statt, Michael J. ;
Blair, Sarah J. ;
Mezzavilla, Stefano ;
Kibsgaard, Jakob ;
Vesborg, Peter C. K. ;
Cargnello, Matteo ;
Bent, Stacey F. ;
Jaramillo, Thomas F. ;
Stephens, Ifan E. L. ;
Norskov, Jens K. ;
Chorkendorff, Ib .
NATURE, 2019, 570 (7762) :504-+
[4]   Feasibility of N2 Binding and Reduction to Ammonia on Fe-Deposited MoS2 2D Sheets: A DFT Study [J].
Azofra, Luis Miguel ;
Sun, Chenghua ;
Cavallo, Luigi ;
MacFarlane, Douglas R. .
CHEMISTRY-A EUROPEAN JOURNAL, 2017, 23 (34) :8275-8279
[5]   Promising prospects for 2D d2-d4 M3C2 transition metal carbides (MXenes) in N2 capture and conversion into ammonia [J].
Azofra, Luis Miguel ;
Li, Neng ;
MacFarlane, Douglas R. ;
Sun, Chenghua .
ENERGY & ENVIRONMENTAL SCIENCE, 2016, 9 (08) :2545-2549
[6]   On the mechanism of electrochemical ammonia synthesis on the Ru catalyst [J].
Back, Seoin ;
Jung, Yousung .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2016, 18 (13) :9161-9166
[7]   Electrochemical Barriers Made Simple [J].
Chan, Karen ;
Norskov, Jens K. .
JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2015, 6 (14) :2663-2668
[8]   Potential Dependence of Electrochemical Barriers from ab Initio Calculations [J].
Chant, Karen ;
Norskov, Jens K. .
JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2016, 7 (09) :1686-1690
[9]   Mechanism and kinetics for both thermal and electrochemical reduction of N2 catalysed by Ru(0001) based on quantum mechanics [J].
Chen, Liang-Yu ;
Kuo, Tung-Chun ;
Hong, Zih-Siang ;
Cheng, Mu-Jeng ;
Goddard, William A., III .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2019, 21 (32) :17605-17612
[10]   Reaction Mechanisms for the Electrochemical Reduction of CO2 to CO and Formate on the Cu(100) Surface at 298 K from Quantum Mechanics Free Energy Calculations with Explicit Water [J].
Cheng, Tao ;
Xiao, Hai ;
Goddard, William A., III .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (42) :13802-13805