TY - JOUR
T1 - Enhanced Electrocatalytic N2 Reduction via Partial Anion Substitution in Titanium Oxide–Carbon Composites
AU - Qin, Qing
AU - Zhao, Yun
AU - Schmallegger, Max
AU - Heil, Tobias
AU - Schmidt, Johannes
AU - Walczak, Ralf
AU - Gescheidt-Demner, Georg
AU - Jiao, Haijun
AU - Oschatz, Martin
PY - 2019/9/9
Y1 - 2019/9/9
N2 - The electrochemical conversion of N2 at ambient conditions using renewably generated electricity is an attractive approach for sustainable ammonia (NH3) production. Considering the chemical inertness of N2, rational design of efficient and stable catalysts is required. Therefore, in this work, it is demonstrated that a C-doped TiO2/C (C-TixOy/C) material derived from the metal–organic framework (MOF) MIL-125(Ti) can achieve a high Faradaic efficiency (FE) of 17.8 %, which even surpasses most of the established noble metal-based catalysts. On the basis of the experimental results and theoretical calculations, the remarkable properties of the catalysts can be attributed to the doping of carbon atoms into oxygen vacancies (OVs) and the formation of Ti−C bonds in C-TixOy. This binding motive is found to be energetically more favorable for N2 activation compared to the non-substituted OVs in TiO2. This work elucidates that electrochemical N2 reduction reaction (NRR) performance can be largely improved by creating catalytically active centers through rational substitution of anions into metal oxides.
AB - The electrochemical conversion of N2 at ambient conditions using renewably generated electricity is an attractive approach for sustainable ammonia (NH3) production. Considering the chemical inertness of N2, rational design of efficient and stable catalysts is required. Therefore, in this work, it is demonstrated that a C-doped TiO2/C (C-TixOy/C) material derived from the metal–organic framework (MOF) MIL-125(Ti) can achieve a high Faradaic efficiency (FE) of 17.8 %, which even surpasses most of the established noble metal-based catalysts. On the basis of the experimental results and theoretical calculations, the remarkable properties of the catalysts can be attributed to the doping of carbon atoms into oxygen vacancies (OVs) and the formation of Ti−C bonds in C-TixOy. This binding motive is found to be energetically more favorable for N2 activation compared to the non-substituted OVs in TiO2. This work elucidates that electrochemical N2 reduction reaction (NRR) performance can be largely improved by creating catalytically active centers through rational substitution of anions into metal oxides.
KW - ammonia synthesis
KW - anion substitution
KW - MOF-derived catalysts
KW - N fixation
KW - non-noble metal catalysts
UR - http://www.scopus.com/inward/record.url?scp=85071786403&partnerID=8YFLogxK
U2 - 10.1002/anie.201906056
DO - 10.1002/anie.201906056
M3 - Article
C2 - 31257671
AN - SCOPUS:85071786403
SN - 1433-7851
VL - 58
SP - 13101
EP - 13106
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 37
ER -