无机材料学报 ›› 2024, Vol. 39 ›› Issue (7): 845-852.DOI: 10.15541/jim20230549
• 研究快报 • 上一篇
收稿日期:
2023-11-30
修回日期:
2024-02-06
出版日期:
2024-07-20
网络出版日期:
2024-03-05
通讯作者:
朱永福, 教授. E-mail: yfzhu@jlu.edu.cn;作者简介:
靳宇翔(1999-), 男, 硕士研究生. E-mail: jinyx21@mails.jlu.edu.cn
JIN Yuxiang1(), SONG Erhong2(
), ZHU Yongfu1(
)
Received:
2023-11-30
Revised:
2024-02-06
Published:
2024-07-20
Online:
2024-03-05
Contact:
ZHU Yongfu, professor. E-mail: yfzhu@jlu.edu.cn;About author:
JIN Yuxiang (1999-), male, Master candidate. E-mail: jinyx21@mails.jlu.edu.cn
Supported by:
摘要:
将CO2高效转化为有价值的化学品(如CO和HCOOH等)是缓解环境问题、实现碳中和的重要措施。然而CO2还原反应(CO2RR)有着产物多样和路径复杂的特点, 再加上目前难以确定影响CO2RR活性的真正因素, 使得设计对特定产物有高选择性和高活性的催化剂十分具有挑战性。本研究从第一性原理出发, 系统研究了3d过渡金属单原子掺杂石墨烯单个空位(TM@CSV)和双空位(TM@CDV)电催化还原CO2的潜力, 具体涵盖基底的稳定性、中间产物热力学吸附以及与之竞争的析氢反应(HER)。通过对Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu和Zn掺杂石墨烯缺陷后形成的20种催化剂进行筛选, 发现Sc原子掺杂石墨烯单个空位的Sc@CSV和Sc、Ti原子掺杂石墨烯双空位的Sc@CDV和Ti@CDV同时具备吸附CO2分子和抑制HER的能力。其中Sc@CDV对HCOOH表现出最佳的活性和选择性, 速率决定步骤的吉布斯自由能差仅为0.96 eV。最后, 通过电子结构分析进一步揭示了Sc@CDV优于其他催化剂的原因是Sc@CDV调整了费米能级附近的活性电子态, 从而实现对CO2的高效还原。
中图分类号:
靳宇翔, 宋二红, 朱永福. 3d过渡金属单原子掺杂石墨烯缺陷电催化还原CO2的第一性原理研究[J]. 无机材料学报, 2024, 39(7): 845-852.
JIN Yuxiang, SONG Erhong, ZHU Yongfu. First-principles Investigation of Single 3d Transition Metals Doping Graphene Vacancies for CO2 Electroreduction[J]. Journal of Inorganic Materials, 2024, 39(7): 845-852.
TM@CSV | Max length of TM-C/Å | Bader charge/|e| |
---|---|---|
Sc@CSV | 2.08 | +1.50 |
Ti@CSV | 1.94 | +1.37 |
V@CSV | 1.89 | +1.22 |
Cr@CSV | 1.86 | +1.35 |
Mn@CSV | 1.83 | +1.00 |
Fe@CSV | 1.76 | +0.67 |
Co@CSV | 1.76 | +0.72 |
Ni@CSV | 1.79 | +0.63 |
Cu@CSV | 1.89 | +0.02 |
Zn@CSV | 1.96 | +0.76 |
Table S1 Max lengthes of TM-C and Bader charges of TM for TM@CSV
TM@CSV | Max length of TM-C/Å | Bader charge/|e| |
---|---|---|
Sc@CSV | 2.08 | +1.50 |
Ti@CSV | 1.94 | +1.37 |
V@CSV | 1.89 | +1.22 |
Cr@CSV | 1.86 | +1.35 |
Mn@CSV | 1.83 | +1.00 |
Fe@CSV | 1.76 | +0.67 |
Co@CSV | 1.76 | +0.72 |
Ni@CSV | 1.79 | +0.63 |
Cu@CSV | 1.89 | +0.02 |
Zn@CSV | 1.96 | +0.76 |
TM@CDV | Max length of TM-C/Å | Bader charge/|e| |
---|---|---|
Sc@CDV | 2.24 | +1.32 |
Ti@CDV | 2.07 | +0.94 |
V@CDV | 2.02 | +1.22 |
Cr@CDV | 2.01 | +0.93 |
Mn@CDV | 1.99 | +0.64 |
Fe@CDV | 1.97 | +0.61 |
Co@CDV | 1.95 | +0.34 |
Ni@CDV | 1.91 | +0.18 |
Cu@CDV | 1.90 | +0.18 |
Zn@CDV | 1.93 | +0.10 |
Table S2 Max lengthes of TM-C and Bader charges of TM for TM@CDV
TM@CDV | Max length of TM-C/Å | Bader charge/|e| |
---|---|---|
Sc@CDV | 2.24 | +1.32 |
Ti@CDV | 2.07 | +0.94 |
V@CDV | 2.02 | +1.22 |
Cr@CDV | 2.01 | +0.93 |
Mn@CDV | 1.99 | +0.64 |
Fe@CDV | 1.97 | +0.61 |
Co@CDV | 1.95 | +0.34 |
Ni@CDV | 1.91 | +0.18 |
Cu@CDV | 1.90 | +0.18 |
Zn@CDV | 1.93 | +0.10 |
Fig. 1 Analyses for Sc@CDV (a) Structure of Sc@CDV; (b) Charge density difference of Sc@CDV with an isovalue of 0.005 e/Å3 (positive and negative charges are shown in green and yellow); (c) PDOS diagram of Sc@CDV; (d) AIMD simulations of Sc@CDV (purple: Sc, brown: C); Colorful figures are available on website
Fig. 2 Structure of H+ adsorption on Sc@CDV (a) and energy changes of H+ adsorption on TM@C (b) Green in (a): H; Colorful figures are available on website
Fig. 3 Gibbs free energy profiles and the competitive reaction analysis (a-c) Free energies of Sc@CSV (a), Sc@CDV (b) and Ti@CDV (c); (d) CO2RR vs HER for TM@C; Colorful figures are available on website
Fig. 4 Electron distributions of Ti@CDV, Sc@CSV and Sc@CDV (a-c) PDOS of Ti@CDV (a), Sc@CSV (b) and Sc@CDV (c) (Gray dashed lines mark the positions of the Fermi energy levels); (d) Eb(*HCOOH) and Eb(*CO2) of Ti@CDV, Sc@CSV and Sc@CDV; The d-band center as an average of the d-band energies; Colorful figures are available on website
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