PMID- 37001674
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20230514
LR  - 20230514
IS  - 1879-1026 (Electronic)
IS  - 0048-9697 (Linking)
VI  - 878
DP  - 2023 Jun 20
TI  - Electrochemical nitrate reduction to high-value ammonia on two-dimensional 
      molybdenum carbide nanosheets for nitrate-containing wastewater upcycling.
PG  - 163145
LID - S0048-9697(23)01764-3 [pii]
LID - 10.1016/j.scitotenv.2023.163145 [doi]
AB  - Electrochemical conversion of nitrate wastewater into high-value ammonia 
      fertilizer has attracted extensive attention in wastewater treatment and resource 
      recovery, but presents great challenges due to complicated reaction pathways and 
      competing side reactions. Herein, we report a feasible method for the successful 
      fabrication of Mo(2)C nanosheets (Mo(2)C NSs) as electrocatalyst for the 
      electroreduction of nitrate to ammonia. Compared to Mo(2)C nanoparticles, the 
      Mo(2)C NSs exhibited superior activity and selectivity in NH(3) electrosynthesis 
      with an NH(3) yield rate of 25.2 mg.h(-1).mg(-1)(cat.) at -0.4 V and a Faradaic 
      efficiency of 81.4 % at -0.3 V versus reversible hydrogen electrode. The X-ray 
      diffraction and transmission electron microscopy characterization verifted the 
      controllable conversion of 2D MoO(2) NSs into 2D Mo(2)C NSs. In situ 
      spectroscopic studies and on-line differential electrochemical mass spectrometry 
      revealed the proposed reaction pathway of NO(3)(-) to NH(3) conversion, *NO(3)(-) 
      --> *NO(2)(-) --> *NO-->*NOH --> *NH(2)OH --> *NH(3). Density functional theory 
      calculations further verified the effective N-end NOH pathway with the conversion 
      of *NH(2)OH to *NH(2) as the rate-determining step requiring a low energy barrier 
      of 0.58 eV. Importantly, the key hydrogenation of *NO to form *NOH species 
      underwent a lower energy barrier of 0.39 eV compared with the formation of *ONH 
      species (1.06 eV).
CI  - Copyright (c) 2023 The Authors. Published by Elsevier B.V. All rights reserved.
FAU - Zhu, Donglin
AU  - Zhu D
AD  - School of the Environment, Nanjing University, Nanjing 210023, PR China.
FAU - Li, Guoguang
AU  - Li G
AD  - School of the Environment, Nanjing University, Nanjing 210023, PR China.
FAU - Yan, Xu
AU  - Yan X
AD  - Huizhou Innovation Research Institute of Next Generation Industrial Internet, 
      Huizhou 516006, PR China.
FAU - Geng, Chunxia
AU  - Geng C
AD  - Beijing Water Planning Institute, Beijing 100089, PR China.
FAU - Gao, Li
AU  - Gao L
AD  - Institute for Sustainable Industries and Liveable Cities, Victoria University, PO 
      Box 14428, Melbourne, Victoria 8001, Australia. Electronic address: 
      Li.gao@vu.edu.au.
LA  - eng
PT  - Journal Article
DEP - 20230329
PL  - Netherlands
TA  - Sci Total Environ
JT  - The Science of the total environment
JID - 0330500
SB  - IM
OTO - NOTNLM
OT  - Ammonia electrosynthesis
OT  - Electrocatalysis
OT  - Electrochemical nitrate reduction
OT  - Molybdenum carbide
OT  - Nitrate wastewater upcycling
COIS- Declaration of competing interest The authors declare that they have no known 
      competing financial interests or personal relationships that could have appeared 
      to influence the work reported in this paper.
EDAT- 2023/04/01 06:00
MHDA- 2023/04/01 06:01
CRDT- 2023/03/31 19:30
PHST- 2023/02/15 00:00 [received]
PHST- 2023/03/24 00:00 [revised]
PHST- 2023/03/25 00:00 [accepted]
PHST- 2023/04/01 06:01 [medline]
PHST- 2023/04/01 06:00 [pubmed]
PHST- 2023/03/31 19:30 [entrez]
AID - S0048-9697(23)01764-3 [pii]
AID - 10.1016/j.scitotenv.2023.163145 [doi]
PST - ppublish
SO  - Sci Total Environ. 2023 Jun 20;878:163145. doi: 10.1016/j.scitotenv.2023.163145. 
      Epub 2023 Mar 29.