(560bg) Copper-Nitrogen-Doped Carbon Nanostructures for an Efficient CO2 Reduction Reaction
AIChE Annual Meeting
2019
2019 AIChE Annual Meeting
Catalysis and Reaction Engineering Division
Poster Session: Catalysis and Reaction Engineering (CRE) Division
Wednesday, November 13, 2019 - 3:30pm to 5:00pm
Copper-Nitrogen-Doped Carbon
Nanostructures for an Efficient CO2 Reduction Reaction Huiyuan Cheng, Xuemei
Wu*, Gaohong He* State Key Laboratory of Fine
Chemicals, Research and Development Center of Membrane Science and Technology,
School of Chemical Engineering, Dalian University of Technology, Dalian, P. R.
China *Corresponding author: Email: xuemeiw@dlut.edu.cn hgaohong@dlut.edu.cn Abstract Electrochemical reduction of carbon dioxide (CO2RR) to
value-added carbon products is an effective approach to fuels generation and CO2
remediation1,2. However, this desired
technology is confronted many challenges as the inert property of CO2 causes extremely
high overpotential and the competitive hydrogen
evolution (HER) side reaction1,3,4. Among studied catalyst
formulations, transition metal and nitrogen doped carbon (M-N-C) nanomaterials have been emerging as promising electrocatalysts for its superiority in low cost and excellent electrocatalytic activity5-7.
Herein, we propose a facile but efficient strategy to facilitate the CO2RR
through rationally tailoring the coordination environment between copper and
nitrogen atoms embedded in porous carbon matrix, which derived from pyrolyzing Cu-doped zeolitic imidazolate frameworks-8(ZIF-8). Figure 1 shows the preparation
scheme of Cu-N-C CO2RR electrocatalysts. Cu2+
ions were controllable doping into ZIF-8 frameworks, followed by calcination in inert atmosphere. The obtained porous carbon nanomaterials inherited
rhombic dodecahedron shape and used directly as CO2RR electrocatalysts
without any acid etching. The Cu-N-C catalyst with optimal structural and
chemical configuration was achieved through investigating pyrolysis
temperature and Cu doping contents. As shown in Figure 2, the optimized Cu-N-C
catalyst exhibits particularly high selectivity with CO faradaic
efficiency over 90% in the potential range from -0.6 to -1.1V (vs. the RHE) and reaches the maximum
value of 98.3% at -0.9V(vs. the RHE) with a current density of 7.3 mAcm-2. Both experimental and
theoretical calculations demonstrate that a hybrid Cu coordination site of Cu0/Cu(II)-N is more beneficial to CO2 activation
than hydrogen evolution reaction. The result provides a significant guideline
to the design of high efficiency CO2 reduction electrocatalysts.
Fig. 1 Schematic illustration
of the synthesis procedure.
Fig. 2 Performance of Cu-N-C electrocatalyst and N-C (pyrolyzed ZIF8).
(a) Linear sweep voltammetric curves in the Ar (dotted line) or CO2-saturated (solid line)
0.1M KHCO3 aqueous solutions with a 5mv s-1 scan rate.
(b) CO Faradaic efficiencies and particial
current density on
applied potencial. Acknowledgment We acknowledge financial contribution from National
Natural Science Foundation of China (Grant No. U1663223, 21776034), Changjiang
Scholars Program (T2012049) References 1. Pan Y, Lin R, Chen Y, et al.
Design of Single-Atom Co-N-5 Catalytic Site: A Robust Electrocatalyst for CO2
Reduction with Nearly 100% CO Selectivity and Remarkable Stability. Journal of the American Chemical Society. Mar 28
2018;140(12):4218-4221. 2.
Yan C, Li H, Ye Y, et al. Coordinatively unsaturated nickel-nitrogen sites
towards selective and high-rate CO2 electroreduction. Energy & Environmental Science. May 1 2018;11(5):1204-1210. 3.
Pan F, Zhang H, Liu K, et al. Unveiling Active Sites of CO2 Reduction on
Nitrogen-Coordinated and Atomically Dispersed Iron and Cobalt Catalysts. Acs Catalysis. Apr 2018;8(4):3116-3122. 4.
Li X, Bi W, Chen M, et al. Exclusive Ni-N-4 Sites Realize Near-Unity CO
Selectivity for Electrochemical CO2 Reduction. Journal of the American Chemical Society. Oct 25
2017;139(42):14889-14892. 5.
Lu P, Yang Y, Yao J, et al. Facile synthesis of single-nickel-atomic
dispersed N-doped carbon framework for efficient electrochemical CO2 reduction.
Applied Catalysis B-Environmental. Feb 2019;241:113-119. 6.
Yin P, Yao T, Wu Y, et al. Single Cobalt Atoms with Precise N-Coordination
as Superior Oxygen Reduction Reaction Catalysts. Angewandte Chemie-International Edition. Aug 26
2016;55(36):10800-10805. 7.
Lai Q, Zheng L, Liang Y, He J, Zhao J, Chen J.
Meta-Organic-Framework-Derived Fe-N/C Electrocatalyst with Five-Coordinated
Fe-N-x), Sites for Advanced Oxygen Reduction in Acid Media. Acs Catalysis. Mar 2017;7(3):1655-1663.
Nanostructures for an Efficient CO2 Reduction Reaction Huiyuan Cheng, Xuemei
Wu*, Gaohong He* State Key Laboratory of Fine
Chemicals, Research and Development Center of Membrane Science and Technology,
School of Chemical Engineering, Dalian University of Technology, Dalian, P. R.
China *Corresponding author: Email: xuemeiw@dlut.edu.cn hgaohong@dlut.edu.cn Abstract Electrochemical reduction of carbon dioxide (CO2RR) to
value-added carbon products is an effective approach to fuels generation and CO2
remediation1,2. However, this desired
technology is confronted many challenges as the inert property of CO2 causes extremely
high overpotential and the competitive hydrogen
evolution (HER) side reaction1,3,4. Among studied catalyst
formulations, transition metal and nitrogen doped carbon (M-N-C) nanomaterials have been emerging as promising electrocatalysts for its superiority in low cost and excellent electrocatalytic activity5-7.
Herein, we propose a facile but efficient strategy to facilitate the CO2RR
through rationally tailoring the coordination environment between copper and
nitrogen atoms embedded in porous carbon matrix, which derived from pyrolyzing Cu-doped zeolitic imidazolate frameworks-8(ZIF-8). Figure 1 shows the preparation
scheme of Cu-N-C CO2RR electrocatalysts. Cu2+
ions were controllable doping into ZIF-8 frameworks, followed by calcination in inert atmosphere. The obtained porous carbon nanomaterials inherited
rhombic dodecahedron shape and used directly as CO2RR electrocatalysts
without any acid etching. The Cu-N-C catalyst with optimal structural and
chemical configuration was achieved through investigating pyrolysis
temperature and Cu doping contents. As shown in Figure 2, the optimized Cu-N-C
catalyst exhibits particularly high selectivity with CO faradaic
efficiency over 90% in the potential range from -0.6 to -1.1V (vs. the RHE) and reaches the maximum
value of 98.3% at -0.9V(vs. the RHE) with a current density of 7.3 mAcm-2. Both experimental and
theoretical calculations demonstrate that a hybrid Cu coordination site of Cu0/Cu(II)-N is more beneficial to CO2 activation
than hydrogen evolution reaction. The result provides a significant guideline
to the design of high efficiency CO2 reduction electrocatalysts.
Fig. 1 Schematic illustrationof the synthesis procedure.
Fig. 2 Performance of Cu-N-C electrocatalyst and N-C (pyrolyzed ZIF8).(a) Linear sweep voltammetric curves in the Ar (dotted line) or CO2-saturated (solid line)
0.1M KHCO3 aqueous solutions with a 5mv s-1 scan rate.
(b) CO Faradaic efficiencies and particial
current density on
applied potencial. Acknowledgment We acknowledge financial contribution from National
Natural Science Foundation of China (Grant No. U1663223, 21776034), Changjiang
Scholars Program (T2012049) References 1. Pan Y, Lin R, Chen Y, et al.
Design of Single-Atom Co-N-5 Catalytic Site: A Robust Electrocatalyst for CO2
Reduction with Nearly 100% CO Selectivity and Remarkable Stability. Journal of the American Chemical Society. Mar 28
2018;140(12):4218-4221. 2.
Yan C, Li H, Ye Y, et al. Coordinatively unsaturated nickel-nitrogen sites
towards selective and high-rate CO2 electroreduction. Energy & Environmental Science. May 1 2018;11(5):1204-1210. 3.
Pan F, Zhang H, Liu K, et al. Unveiling Active Sites of CO2 Reduction on
Nitrogen-Coordinated and Atomically Dispersed Iron and Cobalt Catalysts. Acs Catalysis. Apr 2018;8(4):3116-3122. 4.
Li X, Bi W, Chen M, et al. Exclusive Ni-N-4 Sites Realize Near-Unity CO
Selectivity for Electrochemical CO2 Reduction. Journal of the American Chemical Society. Oct 25
2017;139(42):14889-14892. 5.
Lu P, Yang Y, Yao J, et al. Facile synthesis of single-nickel-atomic
dispersed N-doped carbon framework for efficient electrochemical CO2 reduction.
Applied Catalysis B-Environmental. Feb 2019;241:113-119. 6.
Yin P, Yao T, Wu Y, et al. Single Cobalt Atoms with Precise N-Coordination
as Superior Oxygen Reduction Reaction Catalysts. Angewandte Chemie-International Edition. Aug 26
2016;55(36):10800-10805. 7.
Lai Q, Zheng L, Liang Y, He J, Zhao J, Chen J.
Meta-Organic-Framework-Derived Fe-N/C Electrocatalyst with Five-Coordinated
Fe-N-x), Sites for Advanced Oxygen Reduction in Acid Media. Acs Catalysis. Mar 2017;7(3):1655-1663.