无机材料学报 ›› 2022, Vol. 37 ›› Issue (10): 1141-1148.DOI: 10.15541/jim20220033
• 研究快报 • 上一篇
吴静1(), 余立兵1, 刘帅帅1, 黄秋艳1, 姜姗姗1, ANTON Matveev2, 王连莉3, 宋二红4(), 肖蓓蓓1()
收稿日期:
2022-01-20
修回日期:
2022-04-06
出版日期:
2022-10-20
网络出版日期:
2022-05-09
通讯作者:
肖蓓蓓, 副教授. E-mail: xiaobb11@mails.jlu.edu.cn;作者简介:
吴静(1998-), 女, 硕士研究生. E-mail: wjjust20@163.com
WU Jing1(), YU Libing1, LIU Shuaishuai1, HUANG Qiuyan1, JIANG Shanshan1, ANTON Matveev2, WANG Lianli3, SONG Erhong4(), XIAO Beibei1()
Received:
2022-01-20
Revised:
2022-04-06
Published:
2022-10-20
Online:
2022-05-09
Contact:
XIAO Beibei, associate professor. E-mail: xiaobb11@mails.jlu.edu.cn;About author:
WU Jing(1998-), female, Master candidate. E-mail: wjjust20@163.com
Supported by:
摘要:
工业上应用哈伯工艺法合成氨过程要求严苛, 需要消耗大量能源且二氧化碳排放量大。因此, 开发在常规环境条件下通过电催化氮还原反应的清洁技术, 对未来可持续的能源转化进程具有重要意义。本研究采用密度泛函理论计算方法, 对TM1N4/TM2嵌入石墨烯的氮还原反应进行了全面研究。在充分考虑活性和稳定性的情况下, 研究结果表明, NiN4/Cr锚定石墨烯通过酶促反应途径表现出最佳的催化活性, 其中第一次加氢为电位决定步骤, 起始电位为0.57 V, 优于商业Ru基材料。此外, 与单一的Cr原子修饰的石墨烯相比, 引入NiN4官能团降低了ΔGmax并提高了电催化性能。根据Mulliken电荷分析, 催化剂的催化活性主要来源于载体和反应中间体之间的电子转移。上述结果为高效合成氨提供了电极候选材料, 进一步深化了相应的电催化机理。
中图分类号:
吴静, 余立兵, 刘帅帅, 黄秋艳, 姜姗姗, ANTON Matveev, 王连莉, 宋二红, 肖蓓蓓. NiN4/Cr修饰的石墨烯电化学固氮电极[J]. 无机材料学报, 2022, 37(10): 1141-1148.
WU Jing, YU Libing, LIU Shuaishuai, HUANG Qiuyan, JIANG Shanshan, ANTON Matveev, WANG Lianli, SONG Erhong, XIAO Beibei. NiN4/Cr Embedded Graphene for Electrochemical Nitrogen Fixation[J]. Journal of Inorganic Materials, 2022, 37(10): 1141-1148.
Fig. 4 Free energy diagrams and the corresponding configuration of the NRR intermediates on NiN4/Cr NRR mechanisms are (a) distal, (b) alternating and (c) enzymatic
Fig. 5 (a-c) Charge variation of the three moieties along the optimal pathway and (d) N-N bond length change in NRR along preferred pathway Moieties 1, 2, 3 represent the graphene substrate, active center, and NRR intermediates, respectively
3d | Sc | Ti | V | Cr | Mn | Fe | Co | Ni |
---|---|---|---|---|---|---|---|---|
Eads(TM2) N2 end-on | -0.22 | -0.36 | -0.62 | -0.72 | -1.02 | -1.07 | -0.89 | -0.59 |
Eads(TM2) N2 side-on | 0.12 | -0.02 | -1.17 | -0.35 | -0.59 | -0.51 | -0.33 | -0.19 |
Eads(TM2) H | 0.75 | 0.20 | -0.18 | -0.14 | -0.19 | -0.20 | -0.22 | -0.38 |
4d | Y | Zr | Nb | Mo | Tc | Ru | Rh | Pd |
Eads(TM2) N2 end-on | -0.14 | -0.22 | -1.05 | -0.70 | -0.73 | -0.99 | -0.73 | -1.30 |
Eads(TM2) N2 side-on | -0.13 | 0.11 | -0.42 | -0.43 | -0.47 | -0.44 | -0.25 | -0.96 |
Eads(TM2) H | 0.78 | 0.25 | -0.87 | -0.38 | 0.51 | -0.11 | -0.33 | -1.06 |
5d | Lu | Hf | Ta | W | Re | Os | Ir | Pt |
Eads(TM2) N2 end-on | -0.21 | -0.35 | -0.60 | -1.57 | -1.23 | -1.30 | -1.08 | -0.52 |
Eads(TM2) N2 side-on | 0.07 | 0.02 | -0.32 | -1.48 | -0.88 | -0.68 | -0.44 | -0.23 |
Eads(TM2) H | 0.65 | -0.01 | -1.33 | -0.92 | -0.88 | -0.81 | -0.87 | -0.99 |
Table S1 Adsorption energies Eads on Mn1N4/TM2 (Eads in eV)
3d | Sc | Ti | V | Cr | Mn | Fe | Co | Ni |
---|---|---|---|---|---|---|---|---|
Eads(TM2) N2 end-on | -0.22 | -0.36 | -0.62 | -0.72 | -1.02 | -1.07 | -0.89 | -0.59 |
Eads(TM2) N2 side-on | 0.12 | -0.02 | -1.17 | -0.35 | -0.59 | -0.51 | -0.33 | -0.19 |
Eads(TM2) H | 0.75 | 0.20 | -0.18 | -0.14 | -0.19 | -0.20 | -0.22 | -0.38 |
4d | Y | Zr | Nb | Mo | Tc | Ru | Rh | Pd |
Eads(TM2) N2 end-on | -0.14 | -0.22 | -1.05 | -0.70 | -0.73 | -0.99 | -0.73 | -1.30 |
Eads(TM2) N2 side-on | -0.13 | 0.11 | -0.42 | -0.43 | -0.47 | -0.44 | -0.25 | -0.96 |
Eads(TM2) H | 0.78 | 0.25 | -0.87 | -0.38 | 0.51 | -0.11 | -0.33 | -1.06 |
5d | Lu | Hf | Ta | W | Re | Os | Ir | Pt |
Eads(TM2) N2 end-on | -0.21 | -0.35 | -0.60 | -1.57 | -1.23 | -1.30 | -1.08 | -0.52 |
Eads(TM2) N2 side-on | 0.07 | 0.02 | -0.32 | -1.48 | -0.88 | -0.68 | -0.44 | -0.23 |
Eads(TM2) H | 0.65 | -0.01 | -1.33 | -0.92 | -0.88 | -0.81 | -0.87 | -0.99 |
3d | Sc | Ti | V | Cr | Mn | Fe | Co | Ni |
---|---|---|---|---|---|---|---|---|
Eads(TM2) N2 end-on | -0.21 | -0.75 | -0.26 | -0.52 | -0.94 | -1.06 | -0.88 | -0.53 |
Eads(TM2) N2 side-on | -0.21 | -0.37 | -0.35 | -0.41 | -0.59 | -0.54 | -0.25 | -0.56 |
Eads(TM2) H | 0.93 | 0.33 | 0.27 | -0.02 | -0.14 | -0.25 | -0.11 | -0.37 |
4d | Y | Zr | Nb | Mo | Tc | Ru | Rh | Pd |
Eads(TM2) N2 end-on | -0.14 | -0.22 | -0.20 | -0.62 | -0.88 | -0.96 | -0.76 | -0.49 |
Eads(TM2) N2 side-on | 0.22 | -0.20 | -0.20 | 0.01 | -0.58 | -0.41 | -0.27 | 0.01 |
Eads(TM2) H | 0.90 | 0.21 | 0.17 | -0.23 | -0.12 | -0.12 | -0.09 | -0.33 |
5d | Lu | Hf | Ta | W | Re | Os | Ir | Pt |
Eads(TM2) N2 end-on | -0.20 | -0.31 | -0.64 | -0.91 | -1.15 | -1.27 | -1.09 | -0.26 |
Eads(TM2) N2 side-on | -0.20 | 0.07 | -0.49 | -0.77 | -0.94 | -0.68 | -0.48 | 0.22 |
Eads(TM2) H | 0.77 | 0.01 | -0.73 | -0.84 | -0.68 | -0.78 | -0.72 | -0.99 |
Table S2 Adsorption energies Eads on Fe1N4/TM2 (Eads in eV)
3d | Sc | Ti | V | Cr | Mn | Fe | Co | Ni |
---|---|---|---|---|---|---|---|---|
Eads(TM2) N2 end-on | -0.21 | -0.75 | -0.26 | -0.52 | -0.94 | -1.06 | -0.88 | -0.53 |
Eads(TM2) N2 side-on | -0.21 | -0.37 | -0.35 | -0.41 | -0.59 | -0.54 | -0.25 | -0.56 |
Eads(TM2) H | 0.93 | 0.33 | 0.27 | -0.02 | -0.14 | -0.25 | -0.11 | -0.37 |
4d | Y | Zr | Nb | Mo | Tc | Ru | Rh | Pd |
Eads(TM2) N2 end-on | -0.14 | -0.22 | -0.20 | -0.62 | -0.88 | -0.96 | -0.76 | -0.49 |
Eads(TM2) N2 side-on | 0.22 | -0.20 | -0.20 | 0.01 | -0.58 | -0.41 | -0.27 | 0.01 |
Eads(TM2) H | 0.90 | 0.21 | 0.17 | -0.23 | -0.12 | -0.12 | -0.09 | -0.33 |
5d | Lu | Hf | Ta | W | Re | Os | Ir | Pt |
Eads(TM2) N2 end-on | -0.20 | -0.31 | -0.64 | -0.91 | -1.15 | -1.27 | -1.09 | -0.26 |
Eads(TM2) N2 side-on | -0.20 | 0.07 | -0.49 | -0.77 | -0.94 | -0.68 | -0.48 | 0.22 |
Eads(TM2) H | 0.77 | 0.01 | -0.73 | -0.84 | -0.68 | -0.78 | -0.72 | -0.99 |
3d | Sc | Ti | V | Cr | Mn | Fe | Co | Ni |
---|---|---|---|---|---|---|---|---|
Eads(TM2) N2 end-on | -0.21 | -0.37 | -0.68 | -0.84 | -1.01 | -1.05 | -0.85 | -0.46 |
Eads(TM2) N2 side-on | -0.20 | -0.37 | -0.29 | -0.51 | -0.64 | -0.53 | -0.26 | -0.56 |
Eads(TM2) H | 1.02 | 0.37 | -0.09 | -0.08 | -0.36 | -0.13 | -0.07 | -0.28 |
4d | Y | Zr | Nb | Mo | Tc | Ru | Rh | Pd |
Eads(TM2) N2 end-on | -0.12 | -0.19 | -0.44 | -0.61 | -0.82 | -0.93 | -0.75 | -0.48 |
Eads(TM2) N2 side-on | -0.13 | -0.20 | -0.03 | -0.29 | -0.57 | -0.42 | -0.25 | -0.48 |
Eads(TM2) H | 1.03 | 0.42 | -0.12 | -0.22 | -0.07 | -0.07 | -0.03 | -0.26 |
5d | Lu | Hf | Ta | W | Re | Os | Ir | Pt |
Eads(TM2) N2 end-on | -0.20 | -0.29 | -0.62 | -0.86 | -1.08 | -1.23 | -1.07 | -0.49 |
Eads(TM2) N2 side-on | -0.21 | -0.29 | -0.28 | -0.63 | -0.89 | -0.67 | -0.46 | -0.48 |
Eads(TM2) H | 0.82 | 0.23 | -0.50 | -0.75 | -0.63 | -0.72 | -0.69 | -0.87 |
Table S3 Adsorption energies Eads on Co1N4/TM2 (Eads in eV)
3d | Sc | Ti | V | Cr | Mn | Fe | Co | Ni |
---|---|---|---|---|---|---|---|---|
Eads(TM2) N2 end-on | -0.21 | -0.37 | -0.68 | -0.84 | -1.01 | -1.05 | -0.85 | -0.46 |
Eads(TM2) N2 side-on | -0.20 | -0.37 | -0.29 | -0.51 | -0.64 | -0.53 | -0.26 | -0.56 |
Eads(TM2) H | 1.02 | 0.37 | -0.09 | -0.08 | -0.36 | -0.13 | -0.07 | -0.28 |
4d | Y | Zr | Nb | Mo | Tc | Ru | Rh | Pd |
Eads(TM2) N2 end-on | -0.12 | -0.19 | -0.44 | -0.61 | -0.82 | -0.93 | -0.75 | -0.48 |
Eads(TM2) N2 side-on | -0.13 | -0.20 | -0.03 | -0.29 | -0.57 | -0.42 | -0.25 | -0.48 |
Eads(TM2) H | 1.03 | 0.42 | -0.12 | -0.22 | -0.07 | -0.07 | -0.03 | -0.26 |
5d | Lu | Hf | Ta | W | Re | Os | Ir | Pt |
Eads(TM2) N2 end-on | -0.20 | -0.29 | -0.62 | -0.86 | -1.08 | -1.23 | -1.07 | -0.49 |
Eads(TM2) N2 side-on | -0.21 | -0.29 | -0.28 | -0.63 | -0.89 | -0.67 | -0.46 | -0.48 |
Eads(TM2) H | 0.82 | 0.23 | -0.50 | -0.75 | -0.63 | -0.72 | -0.69 | -0.87 |
3d | Sc | Ti | V | Cr | Mn | Fe | Co | Ni |
---|---|---|---|---|---|---|---|---|
Eads(TM2) N2 end-on | -0.21 | -0.41 | -0.72 | -0.91 | -1.04 | -1.07 | -0.79 | -0.58 |
Eads(TM2) N2 side-on | -0.19 | 0.02 | -0.41 | -0.63 | -0.66 | -0.50 | / | -0.58 |
Eads(TM2) H | 0.97 | 0.19 | -0.14 | -0.40 | -0.23 | -0.22 | -0.18 | -0.27 |
4d | Y | Zr | Nb | Mo | Tc | Ru | Rh | Pd |
Eads(TM2) N2 end-on | -0.12 | -0.24 | -0.51 | -0.70 | -0.91 | -0.98 | -0.73 | -0.48 |
Eads(TM2) N2 side-on | -0.13 | -0.20 | -0.23 | -0.63 | -0.61 | -0.44 | -0.21 | -0.48 |
Eads(TM2) H | 0.97 | 0.15 | -0.33 | -0.22 | -0.12 | -0.13 | -0.16 | -0.25 |
5d | Lu | Hf | Ta | W | Re | Os | Ir | Pt |
Eads(TM2) N2 end-on | -0.20 | -0.33 | -0.74 | -0.98 | -1.17 | -1.30 | -1.06 | -0.65 |
Eads(TM2) N2 side-on | -0.20 | 0.06 | -0.49 | -0.94 | -0.95 | -0.68 | -0.41 | -0.65 |
Eads(TM2) H | 0.85 | 0.02 | -0.71 | -0.66 | -0.69 | -0.82 | -0.81 | -0.93 |
Table S4 Adsorption energies Eads on Ni1N4/TM2 (Eads in eV)
3d | Sc | Ti | V | Cr | Mn | Fe | Co | Ni |
---|---|---|---|---|---|---|---|---|
Eads(TM2) N2 end-on | -0.21 | -0.41 | -0.72 | -0.91 | -1.04 | -1.07 | -0.79 | -0.58 |
Eads(TM2) N2 side-on | -0.19 | 0.02 | -0.41 | -0.63 | -0.66 | -0.50 | / | -0.58 |
Eads(TM2) H | 0.97 | 0.19 | -0.14 | -0.40 | -0.23 | -0.22 | -0.18 | -0.27 |
4d | Y | Zr | Nb | Mo | Tc | Ru | Rh | Pd |
Eads(TM2) N2 end-on | -0.12 | -0.24 | -0.51 | -0.70 | -0.91 | -0.98 | -0.73 | -0.48 |
Eads(TM2) N2 side-on | -0.13 | -0.20 | -0.23 | -0.63 | -0.61 | -0.44 | -0.21 | -0.48 |
Eads(TM2) H | 0.97 | 0.15 | -0.33 | -0.22 | -0.12 | -0.13 | -0.16 | -0.25 |
5d | Lu | Hf | Ta | W | Re | Os | Ir | Pt |
Eads(TM2) N2 end-on | -0.20 | -0.33 | -0.74 | -0.98 | -1.17 | -1.30 | -1.06 | -0.65 |
Eads(TM2) N2 side-on | -0.20 | 0.06 | -0.49 | -0.94 | -0.95 | -0.68 | -0.41 | -0.65 |
Eads(TM2) H | 0.85 | 0.02 | -0.71 | -0.66 | -0.69 | -0.82 | -0.81 | -0.93 |
System | Mechanisms | N2 adsorption | R1 | R2 | R3 | R4 | R5 | R6 | NH3 desorption |
---|---|---|---|---|---|---|---|---|---|
NiN4/Cr | Distal | -0.41 | 0.98 | -0.28 | 0.17 | -1.08 | -1.09 | -0.23 | 1.04 |
Alternating | -0.41 | 0.98 | 0.05 | -0.31 | -0.25 | -1.29 | -0.71 | 1.04 | |
Enzymatic | -0.10 | 0.57 | 0.16 | -0.56 | -0.12 | -1.51 | -0.38 | 1.04 | |
NiN4/Mo | Distal | -0.27 | 0.92 | -0.08 | -0.22 | -1.14 | -0.71 | -0.20 | 1.04 |
Alternating | -0.27 | 0.92 | 0.16 | -0.56 | 0.06 | -1.52 | -0.49 | 1.04 | |
Enzymatic | -0.11 | 0.60 | 0.18 | -0.89 | 0.50 | -1.54 | -0.44 | 1.04 | |
NiN4/Ta | Distal | -0.18 | 0.69 | -0.37 | -0.06 | -1.22 | -1.02 | 0.22 | 1.04 |
Alternating | -0.18 | 0.69 | 0.05 | -0.88 | 0.11 | -1.78 | 0.05 | 1.04 | |
Enzymatic | 0.04 | 0.11 | -0.23 | -0.70 | 0.58 | -1.70 | -0.04 | 1.04 |
Table S5 Free energy change ΔG (ΔG in eV), Ri stands for the ith protonation step
System | Mechanisms | N2 adsorption | R1 | R2 | R3 | R4 | R5 | R6 | NH3 desorption |
---|---|---|---|---|---|---|---|---|---|
NiN4/Cr | Distal | -0.41 | 0.98 | -0.28 | 0.17 | -1.08 | -1.09 | -0.23 | 1.04 |
Alternating | -0.41 | 0.98 | 0.05 | -0.31 | -0.25 | -1.29 | -0.71 | 1.04 | |
Enzymatic | -0.10 | 0.57 | 0.16 | -0.56 | -0.12 | -1.51 | -0.38 | 1.04 | |
NiN4/Mo | Distal | -0.27 | 0.92 | -0.08 | -0.22 | -1.14 | -0.71 | -0.20 | 1.04 |
Alternating | -0.27 | 0.92 | 0.16 | -0.56 | 0.06 | -1.52 | -0.49 | 1.04 | |
Enzymatic | -0.11 | 0.60 | 0.18 | -0.89 | 0.50 | -1.54 | -0.44 | 1.04 | |
NiN4/Ta | Distal | -0.18 | 0.69 | -0.37 | -0.06 | -1.22 | -1.02 | 0.22 | 1.04 |
Alternating | -0.18 | 0.69 | 0.05 | -0.88 | 0.11 | -1.78 | 0.05 | 1.04 | |
Enzymatic | 0.04 | 0.11 | -0.23 | -0.70 | 0.58 | -1.70 | -0.04 | 1.04 |
Distal | Alternating | Enzymatic | ||||
---|---|---|---|---|---|---|
RDS | ΔGmax | RDS | ΔGmax | RDS | ΔGmax | |
Cr | *N2+H→*NNH | 1.03 | *N2+H→*NNH | 1.03 | *N*N+H→*N*NH | 0.66 |
NiN4/Cr | *N2+H→*NNH | 0.98 | *N2+H→*NNH | 0.98 | *N*N+H→*N*NH | 0.57 |
Mo | *N2+H→*NNH | 1.27 | *N2+H→*NNH | 1.27 | *N*N+H→*N*NH | 0.43 |
NiN4/Mo | *N2+H→*NNH | 0.92 | *N2+H→*NNH | 0.92 | *N*N+H→*N*NH | 0.60 |
Ta | *NNH2+H→*N | 0.72 | *N2+H→*NNH | 0.66 | *NH*NH2+H→*NH2*NH2 | 0.49 |
NiN4/Ta | *N2+H→*NNH | 0.69 | *N2+H→*NNH | 0.69 | *NH*NH2+H→*NH2*NH2 | 0.58 |
Table S6 Potential determining step and its free energy change ΔGmax(ΔGmax in eV)
Distal | Alternating | Enzymatic | ||||
---|---|---|---|---|---|---|
RDS | ΔGmax | RDS | ΔGmax | RDS | ΔGmax | |
Cr | *N2+H→*NNH | 1.03 | *N2+H→*NNH | 1.03 | *N*N+H→*N*NH | 0.66 |
NiN4/Cr | *N2+H→*NNH | 0.98 | *N2+H→*NNH | 0.98 | *N*N+H→*N*NH | 0.57 |
Mo | *N2+H→*NNH | 1.27 | *N2+H→*NNH | 1.27 | *N*N+H→*N*NH | 0.43 |
NiN4/Mo | *N2+H→*NNH | 0.92 | *N2+H→*NNH | 0.92 | *N*N+H→*N*NH | 0.60 |
Ta | *NNH2+H→*N | 0.72 | *N2+H→*NNH | 0.66 | *NH*NH2+H→*NH2*NH2 | 0.49 |
NiN4/Ta | *N2+H→*NNH | 0.69 | *N2+H→*NNH | 0.69 | *NH*NH2+H→*NH2*NH2 | 0.58 |
Fig. S2 Free energy diagrams and the corresponding configuration of the NRR intermediates on NiN4/Mo NRR mechanisms are (a) distal, (b) alternating, and (c) enzymatic, respectively
Fig. S3 Free energy diagrams and the corresponding configuration of the NRR intermediates on NiN4/Ta NRR mechanisms are (a) distal, (b) alternating, and (c) enzymatic, respectively
Fig. S4 Free energy diagrams and the corresponding configuration of the NRR intermediates on Cr embedded nitrogen functionalized graphene NRR mechanisms are (a) distal, (b) alternating, and (c) enzymatic, respectively
Fig. S5 Free energy diagrams and the corresponding configuration of the NRR intermediates on Mo embedded nitrogen functionalized graphene NRR mechanisms are (a) distal, (b) alternating, and (c) enzymatic, respectively
Fig. S6 Free energy diagrams and the corresponding configuration of the NRR intermediates on Ta embedded nitrogen functionalized graphene NRR mechanisms are (a) distal, (b) alternating, and (c) enzymatic, respectively
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