CO2还原和HCHO氧化耦合电催化反应系统高效益生产高附加值产物

doi:10.3866/PKU.WHXB202305028

Abstract

Abstract:

Due to rapid industrial development and human activities, CO₂ emissions have led to serious environmental/ecological problems and climate changes such as global warming. Due to this situation, achieving carbon neutrality has become an urgent mission to improve the future of mankind. The use of the electrocatalytic CO₂ reduction reaction (CO₂RR) to produce higher-value fuels and chemicals is an effective strategy for reducing CO₂ emissions and easing the energy crisis. The water oxidation half-reaction (WOR), which occurs at the anode in a traditional CO₂RR system, typically suffers from slow kinetics, a large overpotential, and high energy consumption. The organic pollutant formaldehyde (HCHO) is oxidized into industrial materials (such as formic acid) under neutral conditions, which is of great significance for the sustainable production of energy and lessening environmental pollution. In addition, the number of electron transfers involved and the required potential for the HCHO oxidation half-reaction (FOR) are smaller than those of WOR, suggesting that FOR could potentially replace WOR as a coupling reaction with CO₂ reduction. In this study, FOR at a MnO₂/CP anode is introduced to produce a novel paired CO₂RR/FOR system. The current density and generation rate of CO₂RR products in this paired CO₂RR/FOR system are generally larger than those of conventional CO₂RR/WOR systems at the same applied potential. Moreover, in paired CO₂RR/FOR systems, HCHO can be selectively converted into HCOOH at certain applied potentials. Nearly 90% of the HCHO can be selectively converted to HCOOH with a conversion efficiency of about 48% at a cell voltage of 3.5 V in a two-electrode paired CO₂RR/FOR system. More significantly, under a different working current, the potentials required for FOR are systemically smaller than those for WOR. At −10 mA∙cm⁻², the cell voltage of the paired CO₂RR/FOR system can be reduced by 210 mV, and the required electric energy for the paired CO₂RR/FOR system can be reduced by 45.13% compared with the sum of single CO₂RR and FOR systems. Notably, when a commercial polysilicon solar cell is used as the power supply, improvements in the current density, the generation rate of CO₂RR products, and the HCHO to HCOOH selectivity can be still achieved in the paired CO₂RR/FOR system. The present work will inspire further studies for developing novel paired CO₂RR systems for the cost-effective, simultaneous conversion of CO₂ and organic pollutants into valuable chemicals.

Key words: CO₂ reduction, HCHO oxidation, Paired electrochemical system, Cu, MnO₂

Xudong Lv, Tao Shao, Junyan Liu, Meng Ye, Shengwei Liu. Paired Electrochemical CO₂ Reduction and HCHO Oxidation for the Cost-Effective Production of Value-Added Chemicals[J]. Acta Phys. -Chim. Sin. 2024, 40(5), 2305028. doi: 10.3866/PKU.WHXB202305028

Figures/Tables 13

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References 46

1	Chen Y. ; Chen C. ; Cao X. ; Wang Z. ; Zhang N. ; Liu T. Acta Phys. -Chim. Sin. 2023, 39, 2212053. doi: 10.3866/PKU.WHXB202212053
	陈瑶; 陈存; 曹雪松; 王震宇; 张楠; 刘天西.. 物理化学学报, 2023, 39, 2212053. doi: 10.3866/PKU.WHXB202212053
2	Han B. Acta Phys. -Chim. Sin. 2022, 38, 2012011. doi: 10.3866/PKU.WHXB202012011
	韩布兴.. 物理化学学报, 2022, 38, 2012011. doi: 10.3866/PKU.WHXB202012011
3	Liu Z. ; Sun Z. Acta Phys. -Chim. Sin. 2021, 37, 2012024. doi: 10.3866/PKU.WHXB202012024
	刘志敏; 孙振宇.. 物理化学学报, 2021, 37, 2012024. doi: 10.3866/PKU.WHXB202012024
4	Shi Y. ; Hou M. ; Li J. ; Li L. ; Zhang Z. Acta Phys. -Chim. Sin. 2022, 38, 2206020. doi: 10.3866/PKU.WHXB202206020
	石永霞; 侯曼; 李俊俊; 李丽; 张志成.. 物理化学学报, 2022, 38, 2206020. doi: 10.3866/PKU.WHXB202206020
5	Yuan Q. ; Yang H. ; Xie M. ; Cheng T. Acta Phys. -Chim. Sin. 2021, 37, 2010040. doi: 10.3866/PKU.WHXB202010040
	苑琦; 杨昊; 谢淼; 程涛.. 物理化学学报, 2021, 37, 2010040. doi: 10.3866/PKU.WHXB202010040
6	Liang Y. ; Wu X. ; Liu X. ; Li C. ; Liu S. Appl. Catal. B: Environ. 2022, 304, 120978. doi: 10.1016/j.apcatb.2021.120978
7	Ye M. ; Shao T. ; Liu J. ; Li C. ; Song B. ; Liu S. Appl. Surf. Sci. 2023, 622, 156981. doi: 10.1016/j.apsusc.2023.156981
8	Xie H. ; Wang T. ; Liang J. ; Li Q. ; Sun S. Nano Today 2018, 21, 41. doi: 10.1016/j.nantod.2018.05.001
9	Gao S. ; Sun Z. ; Liu W. ; Jiao X. ; Zu X. ; Hu Q. ; Sun Y. ; Yao T. ; Zhang W. ; Wei S. ; et al Nat., Commun. 2017, 8, 14503. doi: 10.1038/ncomms14503
10	Ye W. ; Guo X. ; Ma T. Chem. Eng. J. 2021, 414, 128825. doi: 10.1016/j.cej.2021.128825
11	Ma M. ; Djanashvili K. ; Smith W. A. Angew. Chem. Int. Ed. 2016, 55, 6680. doi: 10.1002/anie.201601282
12	Wang J. ; Gan L. ; Zhang Q. ; Reddu V. ; Peng Y. ; Liu Z. ; Xia X. ; Wang C. ; Wang X. Adv. Energy Mater. 2019, 9, 1803151. doi: 10.1002/aenm.201803151
13	Yu N. ; Cao W. ; Huttula M. ; Kayser Y. ; Hoenicke P. ; Beckhoff B. ; Lai F. ; Dong R. ; Sun H. ; Geng B. Appl. Catal. B: Environ. 2020, 261, 118193. doi: 10.1016/j.apcatb.2019.118193
14	Llorente M. J. ; Nguyen B. H. ; Kubiak C. P. ; Moeller K. D. J. Am. Chem. Soc. 2016, 138, 15110. doi: 10.1021/jacs.6b08667
15	Verma S. ; Lu S. ; Kenis P. J. A. Nat. Energy 2019, 4, 466. doi: 10.1038/s41560-019-0374-6
16	Zhang S. ; Zhuo Y. ; Ezugwu C. I. ; Wang C. C. ; Li C. ; Liu S. Environ. Sci. Technol. 2021, 55, 8341. doi: 10.1021/acs.est.1c01277
17	Zhuo Y. ; Guo X. ; Cai W. ; Shao T. ; Xia D. ; Li C. ; Liu S. Appl. Catal. B: Environ. 2023, 333, 122789. doi: 10.1016/j.apcatb.2023.122789
18	Li S. ; Ezugwu C. I. ; Zhang S. ; Xiong Y. ; Liu S. Appl. Surf. Sci. 2019, 487, 260. doi: 10.1016/j.apsusc.2019.05.083
19	Ezugwu C. I. ; Zhang S. ; Li S. ; Shi S. ; Li C. ; Verpoort F. ; Yu J. ; Liu S. Environ. Sci. Nano 2019, 6, 2931. doi: 10.1039/c9en00871c
20	Silva A. M. T. ; Castelo-Branco I. M. ; Quinta-Ferreira R. M. ; Levec J. Chem. Eng. Sci. 2003, 58, 963. doi: 10.1016/s0009-2509(02)00636-x
21	Mei X. ; Guo Z. ; Liu J. ; Bi S. ; Li P. ; Wang Y. ; Shen W. ; Yang Y. ; Wang Y. ; Xiao Y. ; et al Chem. Eng. J. 2019, 372, 673. doi: 10.1016/j.cej.2019.04.184
22	Li G. ; Han G. ; Wang L. ; Cui X. ; Moehring N. K. ; Kidambi P. R. ; Jiang D. E. ; Sun Y. Nat. Commun. 2023, 14, 525. doi: 10.1038/s41467-023-36142-7
23	Liao W. ; Chen Y.-W. ; Liao Y.-C. ; Lin X.-Y. ; Yau S. ; Shyue J.-J. ; Wu S.-Y. ; Chen H.T. Electrochim. Acta 2020, 333, 135542. doi: 10.1016/j.electacta.2019.135542
24	Jin Z. ; Li P. ; Liu G. ; Zheng B. ; Yuan H. ; Xiao D. J. Mater. Chem. A 2013, 1, 14736. doi: 10.1039/c3ta13277c
25	Fukunaga M. T. ; Guimarães J. R. ; Bertazzoli R. Chem. Eng. J. 2008, 136, 236. doi: 10.1016/j.cej.2007.04.006
26	He D. ; Wang G. ; Liu G. ; Bai J. ; Suo H. ; Zhao C. J. Alloy. Compd. 2017, 699, 706. doi: 10.1016/j.jallcom.2016.12.398
27	Babakhani B. ; Ivey D. G. J. Power Sources 2011, 196, 10762. doi: 10.1016/j.jpowsour.2011.08.102
28	Sun M. ; Fang L. M. ; Liu J. Q. ; Zhang F. ; Zhai L. F. Chemosphere 2019, 234, 269. doi: 10.1016/j.chemosphere.2019.06.083
29	Wang Z. ; Jia H. ; Liu Z. ; Peng Z. ; Dai Y. ; Zhang C. ; Guo X. ; Wang T. ; Zhu L. J. Hazard. Mater. 2021, 413, 125285. doi: 10.1016/j.jhazmat.2021.125285
30	Guan S. ; Huang Q. ; Ma J. ; Li W. ; Ogunbiyi A. T. ; Zhou Z. ; Chen K. ; Zhang Q. Ind. Eng. Chem. Res. 2019, 59, 596. doi: 10.1021/acs.iecr.9b05191
31	Huang Y. ; Handoko A. D. ; Hirunsit P. ; Yeo B. S. ACS Catal. 2017, 7, 1749. doi: 10.1021/acscatal.6b03147
32	Sandberg R. B. ; Montoya J. H. ; Chan K. ; Nørskov J. K. Surf. Sci. 2016, 654, 56. doi: 10.1016/j.susc.2016.08.006
33	Ren D. ; Fong J. ; Yeo B. S. Nat. Commun. 2018, 9, 925. doi: 10.1038/s41467-018-03286-w
34	Hu X. ; Hval H. H. ; Bjerglund E. T. ; Dalgaard K. J. ; Madsen M. R. ; Pohl M.-M. ; Welter E. ; Lamagni P. ; Buh K. B. ; Bremholm M. ; et al ACS Catal. 2018, 8, 6255. doi: 10.1021/acscatal.8b01022
35	Chen Y. ; Li C. W. ; Kanan M. W. J. Am. Chem. Soc. 2012, 134, 19969. doi: 10.1021/ja309317u
36	Liu M. ; Pang Y. ; Zhang B. ; De Luna P. ; Voznyy O. ; Xu J. ; Zheng X. ; Dinh C. T. ; Fan F. ; Cao C. ; et al Nature 2016, 537, 382. doi: 10.1038/nature19060
37	Wang J. ; Li J. ; Jiang C. ; Zhou P. ; Zhang P. ; Yu J. Appl. Catal. B: Environ. 2017, 204, 147. doi: 10.1016/j.apcatb.2016.11.036
38	Montoya J. H. ; Shi C. ; Chan K. ; Norskov J. K. J. Phys. Chem. Lett. 2015, 6, 2032. doi: 10.1021/acs.jpclett.5b00722
39	Jin L. ; Seifitokaldani A. Catalysts 2020, 10, 481. doi: 10.3390/catal10050481
40	Rong S. ; He T. ; Zhang P. Appl. Catal. B: Environ. 2020, 267, 118375. doi: 10.1016/j.apcatb.2019.118375
41	Hasanzadeh M. ; Khalilzadeh B. ; Shadjou N. ; Karim-Nezhad G. ; Saghatforoush L. ; Kazeman I. ; Abnosi M. H. Electroanalysis 2010, 22, 168. doi: 10.1002/elan.200900294
42	Li Y. ; Wei X. ; Han S. ; Chen L. ; Shi J. Angew. Chem. Int. Ed. 2021, 60, 21464- 21472. doi: 10.1002/anie.202107510
43	Smith P. F. ; Deibert B. J. ; Kaushik S. ; Gardner G. ; Hwang S. ; Wang H. ; Al-Sharab J. F. ; Garfunkel E. ; Fabris L. ; Li J. ; Dismukes G. C. ACS Catal. 2016, 6, 2089. doi: 10.1021/acscatal.6b00099
44	Ji J. ; Lu X. ; Chen C. ; He M. ; Huang H. Appl. Catal. B: Environ. 2020, 260, 118210. doi: 10.1016/j.apcatb.2019.118210
45	Cho K. H. ; Park S. ; Seo H. ; Choi S. ; Lee M. Y. ; Ko C. ; Nam K. T. Angew. Chem. Int. Ed. 2021, 60, 4673. doi: 10.1002/anie.202014551
46	Subbaraman R. ; Tripkovic D. ; Chang K. C. ; Strmcnik D. ; Paulikas A. P. ; Hirunsit P. ; Chan M. ; Greeley J. ; Stamenkovic V. ; Markovic N. M. Nat. Mater. 2012, 11, 550. doi: 10.1038/nmat3313

E_cell /V	CO₂ RR/WOR system				Paired CO₂ RR/FOR system
E_cell /V	E_anode/V	E_cathode/V		E_IR/V	E_anode/V	E_cathode/V	E_IR/V
2.0	1.05	−0.91	0.04		0.81	−1.11	0.08
2.5	1.15	−1.16	0.19		0.91	−1.23	0.36
3.0	1.19	−1.32	0.49		0.97	−1.39	0.64
3.5	1.26	−1.47	0.77		1.05	−1.52	0.93

J/(mA∙cm⁻²)	E_cathode/V	CO₂RR/WOR			Paired CO₂RR/FOR			E_IR/V	ΔE_cell/V	ΔQ/Q₁ (%)
J/(mA∙cm⁻²)	E_cathode/V	E_cell/V	E_anode/V	Q₁/J	E_cell/V	E_anode/V	Q₂/J	E_IR/V	ΔE_cell/V	ΔQ/Q₁ (%)
−1.00	−1.09	2.28	1.12	12.32	1.99	0.81	10.75	0.08	0.29	12.74
−2.00	−1.16	2.52	1.15	27.22	2.25	0.88	24.30	0.21	0.27	10.71
−3.00	−1.23	2.75	1.18	44.55	2.48	0.91	40.18	0.34	0.27	9.82
−4.00	−1.30	2.94	1.19	63.51	2.67	0.92	57.67	0.45	0.27	9.18
−5.00	−1.36	3.11	1.21	83.97	2.86	0.96	77.22	0.54	0.25	8.04
−6.00	−1.42	3.28	1.23	106.27	3.03	0.98	98.17	0.63	0.25	7.62
−7.00	−1.46	3.44	1.25	130.03	3.21	1.02	121.34	0.73	0.23	6.69
−8.00	−1.49	3.61	1.27	155.95	3.38	1.04	146.02	0.85	0.23	6.37
−9.00	−1.56	3.77	1.28	183.22	3.54	1.05	172.04	0.93	0.23	6.10
−10.00	−1.61	3.93	1.30	212.22	3.72	1.09	200.88	1.02	0.21	5.34
−11.00	−1.65	4.11	1.32	244.13	3.92	1.13	232.85	1.14	0.19	4.62
−12.00	−1.69	4.27	1.34	276.70	4.12	1.19	266.98	1.24	0.15	3.51
−13.00	−1.72	4.43	1.35	310.99	4.33	1.25	303.97	1.36	0.10	2.26
−14.00	−1.76	4.59	1.37	347.00	4.50	1.28	340.2	1.46	0.09	1.96
−16.00	−1.83	4.91	1.40	424.22	4.85	1.34	419.04	1.68	0.06	1.22

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