TY - JOUR
T1 - Regulating the spin state of single-atom doped covalent triazine frameworks for efficient nitrogen fixation
AU - Fang, Lei
AU - Gou, Gaozhang
AU - Shang, Jin
AU - Liu, Mingxian
AU - Gu, Qinfen
AU - Li, Liangchun
PY - 2022/12
Y1 - 2022/12
N2 - Covalent triazine frameworks (CTFs), served as a versatile platform, can form expedient metal–N single-atom coordination sites as promising catalytic centers. To seek out excellent candidate catalysts of M/CTFs (M = Transition metal) for nitrogen reduction reaction (NRR), a “five-step” strategy involving spin states has been established for hierarchical high-throughput screening and reveals strong coordination ability of the CTFs, outstanding conductivity of the M/CTFs, effective adsorption and activation of N2* attributed to the electron transfer and orbital hybridization between the M/CTFs and N2*. Among the potential candidates, the Cr/CTF is screened out to be an excellent one for nitrogen fixation, which can not only inhibit hydrogen evolution reaction (HER) greatly but also has good thermodynamic stability (Eb = −4.40 eV), narrow band gap (Eg = 0.03 eV), moderate adsorption energy (Ea = −0.84 eV), large activation energy (ΔGN2* = −0.71 eV) and a theoretical Faradaic efficiency of 100%. The spin state has been confirmed to be an important descriptor of catalytic activity and the two-state reactivity (TSR) is validated to exist in the NRR. Reaction mechanism with different spin states of Cr/CTF has been demonstrated to give a great impact on the nitrogen fixation, providing solid theoretical support for the design of more efficient NRR catalysts.
AB - Covalent triazine frameworks (CTFs), served as a versatile platform, can form expedient metal–N single-atom coordination sites as promising catalytic centers. To seek out excellent candidate catalysts of M/CTFs (M = Transition metal) for nitrogen reduction reaction (NRR), a “five-step” strategy involving spin states has been established for hierarchical high-throughput screening and reveals strong coordination ability of the CTFs, outstanding conductivity of the M/CTFs, effective adsorption and activation of N2* attributed to the electron transfer and orbital hybridization between the M/CTFs and N2*. Among the potential candidates, the Cr/CTF is screened out to be an excellent one for nitrogen fixation, which can not only inhibit hydrogen evolution reaction (HER) greatly but also has good thermodynamic stability (Eb = −4.40 eV), narrow band gap (Eg = 0.03 eV), moderate adsorption energy (Ea = −0.84 eV), large activation energy (ΔGN2* = −0.71 eV) and a theoretical Faradaic efficiency of 100%. The spin state has been confirmed to be an important descriptor of catalytic activity and the two-state reactivity (TSR) is validated to exist in the NRR. Reaction mechanism with different spin states of Cr/CTF has been demonstrated to give a great impact on the nitrogen fixation, providing solid theoretical support for the design of more efficient NRR catalysts.
KW - Covalent triazine frameworks
KW - High-throughput screening
KW - Nitrogen reduction reaction
KW - Single-atom coordination
KW - Two-state reactivity
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UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85134883472&origin=recordpage
U2 - 10.1016/j.jcis.2022.07.090
DO - 10.1016/j.jcis.2022.07.090
M3 - RGC 21 - Publication in refereed journal
SN - 0021-9797
VL - 627
SP - 931
EP - 941
JO - Journal of Colloid and Interface Science
JF - Journal of Colloid and Interface Science
ER -
