A computational study of electrochemical CO2 reduction to formic acid on metal-doped SnO2

doi:10.1016/S1872-2067(23)64476-6

Abstract

Abstract:

Electrochemical reduction of CO₂ to formic acid (HCOOH) can contribute to the renewable energy transition as a liquid carrier of renewably hydrogen. Here, we investigated the catalytic requirements of SnO₂ electrodes for efficient CO₂ reduction to HCOOH using density functional theory and microkinetics simulations. Hydroxylation of the surface is a prerequisite to achieve a high activity with predicted current densities in agreement with experiment. The resulting surface is selective to HCOOH production with a negligible contribution of the hydrogen evolution reaction. Mechanistically, it is found that the reaction proceeds via hydrogenation of adsorbed CO₂ to carboxylate (COOH), which is then further hydrogenated to the desired product. Doping of the surface by commonly used elements (Bi, Pd, Ni and Cu) identifies Bi as the preferred promoter to substantially improve the current density. Brønsted-Evans-Polanyi relations are established for the two key steps in the mechanism. Overall, carboxylate formation is the rate-controlling step. The CO₂ reduction activity is analyzed in terms of two descriptors, namely the free energies for the two protonation steps, showing that Bi presents the highest activity.

Key words: CO₂ reduction, Formic acid, SnO₂, Promoters, Density functional theory

Zhaochun Liu, Xue Zong, Dionisios G. Vlachos, Ivo A. W. Filot, Emiel J. M. Hensen. A computational study of electrochemical CO₂ reduction to formic acid on metal-doped SnO₂[J]. Chinese Journal of Catalysis, 2023, 50: 249-259.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64476-6

https://www.cjcatal.com/EN/Y2023/V50/I7/249

Figures/Tables 10

Fig. 1. Top view (a) and side view (b) of the SnO2?x(OH)4 model, top view (c) and side view (d) of the most stable adsorption configuration of CO2 on SnO2?x(OH)4 (gray = Sn, red = O atoms of SnO2?x(OH)4, orange = O of CO2, black = C, white = H).

Fig. 3. Top view of the most stable adsorption configuration of CO2RR on SnO2?x(OH)4 (gray = Sn, red = O atoms of SnO2?x(OH)4, orange = O of CO2, black = C, white = H).

Fig. 2. Reaction energy diagram for CO2RR on the SnO2?x(OH)4 surface at standard conditions (T = 298.15 K, P = 1 bar, pH = 0, and 0 V vs. RHE).

Fig. 4. Reaction energy diagram for CO2RR on metal-doped SnO2?x(OH)4 surface at standard conditions (T = 298.15 K, P = 1 bar, pH = 0, and 0 V vs. RHE).

Fig. 5. Br?nsted-Evans-Polanyi plots for CO2 to COOH* step (a) and COOH* to HCOOH step (b) on metal-doped (metal = Ni, Pd, Bi, and Cu) SnO2?x(OH)4 surfaces.

Fig. 6. Correlation matrix between properties of the dopant metal and the reaction energy and activation barrier for the elementary reaction step CO2* + H* → COOH* + *. Positive values indicate positive correlations, while negatives ones anticorrelations between the parameters.

Fig. 7. Microkinetics simulations of electrochemical CO2RR on undoped and Bi-doped SnO2?x(OH)4 surfaces using a reaction-diffusion model pertaining to a rotating disc electrode setup operated at 100 r/min with a bulk pH of 6.8. (a) Total electrochemical current; (b) Near-surface concentration of CO2; (c) Near-surface concentration of H+; (d) Faradaic efficiency of various product.

Fig. 8. Evolution of surface coverages during electrochemical CO2RR on the SnO2?x(OH)4 surface on a rotating disc electrode at 100 r/min and a bulk pH of 6.8.

Fig. 9. The degree of rate control coefficients during electrochemical CO2RR on the SnO2?x(OH)4 surface on a rotating disc electrode at 100 r/min and a bulk pH of 6.8.

Fig. 10. Heatmap of the TOF as a function of ΔG*COOH ? ΔG*CO2 and ΔG*HCOOH ? ΔG*COOH adsorption energies for electrocatalytic CO2RR on metal doped SnO2?x(OH)4 surface based on DFT-based microkinetic simulations at ?0.2 V vs. RHE. Reaction conditions are T = 300 K on a rotating disc electrode at 100 r/min and a bulk pH of 6.8.

References

[1]	S. Gao, Y. Lin, X. Jiao, Y. Sun, Q. Luo, W. Zhang, D. Li, J. Yang, Y. Xie, Nature, 2016, 529, 68-71.
[2]	M. Asadi, K. Kim, C. Liu, A. V Addepalli, P. Abbasi, P. Yasaei, P. Phillips, A. Behranginia, J. M. Cerrato, R. Haasch, P. Zapol, B. Kumar, R. F. Klie, J. Abiade, L. A. Curtiss, A. Salehi-Khojin, Science, 2016, 353, 467-470.
[3]	J. Qiao, Y. Liu, F. Hong, J. Zhang, Chem. Soc. Rev. 2014, 43, 631-675.
[4]	L. Zhang, Z. J. Zhao, J. Gong, Angew. Chem., Int. Ed. 2017, 56, 11326-11353.
[5]	X. Yuan, L. Zhang, L. Li, H. Dong, S. Chen, W. Zhu, C. Hu, W. Deng, Z. J. Zhao, J. Gong, J. Am. Chem. Soc. 2019, 141, 4791-4794.
[6]	D. Kim, J. Resasco, Y. Yu, A. M. Asiri, P. Yang, Nat. Commun. 2014, 5, 4948.
[7]	M. Grasemann, G. Laurenczy, Energy Environ. Sci. 2012, 5, 8171-8181.
[8]	Y. Zhang, L. Chen, F. Li, C. D. Easton, J. Li, A. M. Bond, Y. Zhang, ACS Catal. 2017, 7, 4846-4853.
[9]	Y. Zhang, F. Li, X. Zhang, T. Williams, C. D. Easton, A. M. Bond, J. Zhang, J. Mater. Chem. A, 2018, 6, 4714-4720.
[10]	C. W. Lee, J. S. Hong, K. D. Yang, K. Jin, J. H. Lee, H.-Y. Ahn, H. Seo, N.-E. Sung, K. T. Nam, ACS Catal. 2018, 8, 931-937.
[11]	Z. M. Detweiler, J. L. White, S. L. Bernasek, A. B. Bocarsly, Langmuir, 2014, 30, 7593-7600.
[12]	J. Zhang, R. Yin, Q. Shao, T. Zhu, X. Huang, Angew. Chem. Int. Ed. 2019, 58, 5609-5613.
[13]	C. I. Shaughnessy, D. T. Jantz, K. C. Leonard, J. Mater. Chem. A, 2017, 5, 22743-22749.
[14]	G. Liu, Z. Li, J. Shi, K. Sun, Y. Ji, Z. Wang, Y. Qiu, Y. Liu, Z. Wang, P. Hu, Appl. Catal. B, 2020, 260, 118134.
[15]	Y. Wei, J. Liu, F. Cheng, J. Chen, J. Mater. Chem. A, 2019, 7, 19651-19656.
[16]	J. E. Pander, M. F. Baruch, A. B. Bocarsly, ACS Catal. 2016, 6, 7824-7833.
[17]	F. Lei, W. Liu, Y. Sun, J. Xu, K. Liu, L. Liang, T. Yao, B. Pan, S. Wei, Y. Xie, Nat. Commun. 2016, 7, 12697.
[18]	Y. Hori, I. Takahashi, O. Koga, N. Hoshi, J. Phys. Chem. B, 2002, 106, 15-17.
[19]	F. Koleli, T. Atilan, N. Palamut, A. Gizir, R. Aydin, C. H. Hamann, J. Appl. Electrochem. 2003, 33, 447-450.
[20]	C. Oloman, H. Li, ChemSusChem, 2008, 1, 385-391.
[21]	Y. Chen, M. W. Kanan, J. Am. Chem. Soc. 2012, 134, 1986-1989.
[22]	S. Zhang, P. Kang, T. J. Meyer, J. Am. Chem. Soc. 2014, 136, 1734-1737.
[23]	Z. Chen, T. Fan, Y. Q. Zhang, J. Xiao, M. Gao, N. Duan, J. Zhang, J. Li, Q. Liu, X. Yi, J. L. Luo, Appl. Catal. B, 2020, 261,118243.
[24]	W. Deng, L. Zhang, L. Li, S. Chen, C. Hu, Z. J. Zhao, T. Wang, J. Gong, J. Am. Chem. Soc. 2019, 141, 2911-2915.
[25]	C. Cui, J. Han, X. Zhu, X. Liu, H. Wang, D. Mei, Q. Ge, J. Catal. 2016, 343, 257-265.
[26]	A. Dutta, A. Kuzume, M. Rahaman, S. Vesztergom, P. Broekmann, ACS Catal. 2015, 5, 7498-7502.
[27]	J. T. Feaster, C. Shi, E. R. Cave, T. Hatsukade, D. N. Abram, K. P. Kuhl, C. Hahn, J. K. Nørskov, T. F. Jaramillo, ACS Catal. 2017, 7, 4822-4827.
[28]	L. Li, Z.-J. Zhao, C. Hu, P. Yang, X. Yuan, Y. Wang, L. Zhang, L. Moskaleva, J. Gong, ACS Energy Lett. 2020, 5, 552-558.
[29]	G. Kresse, J. Furthmuller, J. Hafner, Phys. Rev. B, 1994, 50, 13181-13185.
[30]	P. E. Blochl, Phys. Rev. B, 1994, 50, 17953-17979.
[31]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. B, 1996, 3865-3868.
[32]	S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys. 2010, 132, 154104.
[33]	J. K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. R. Kitchin, T. Bligaard, H. Jónsson, J. Phys. Chem. B, 2004, 108, 17886-17892.
[34]	K. Mathew, R. Sundararaman, K. Letchworth-Weaver, T. A. Arias, R. G. Hennig, J. Chem. Phys. 2014, 140, 084106.
[35]	S. Yang, Z. Liu, H. An, S. Arnouts, J. de Ruiter, F. Rollier, S. Bals, T. Altantzis, M. C. Figueiredo, I. A. W. Filot, E. J. M. Hensen, B. M. Weckhuysen, W. van der Stam, ACS Catal. 2022, 12, 15146-15156.
[36]	M. Chase, J. Phys. Chem. Ref. Data, 1998, 27(6), I-II.
[37]	G. Rostamikia, A. J. Mendoza, M. A. Hickner, M. J. Janik, J. Power Sources, 2011, 196, 9228-9237.
[38]	S. A. Akhade, N. J. Bernstein, M. R. Esopi, M. J. Regula, M. J. Janik, Catal. Today, 2017, 288, 63-73.
[39]	D. Luan, J. Xiao, J. Phys. Chem. Lett. 2023, 14, 685-693.
[40]	X. Liu, P. Schlexer, J. Xiao, Y. Ji, L. Wang, R. B. Sandberg, M. Tang, K. S. Brown, H. Peng, S. Ringe, C. Hahn, T. F. Jaramillo, J. K. Nørskov, K. Chan, Nat. Commun. 2019, 10, 32.
[41]	L. Wang, S. A. Nitopi, E. Bertheussen, M. Orazov, C. G. Morales-Guio, X. Liu, D. C. Higgins, K. Chan, J. K. Nørskov, C. Hahn, T. F. Jaramillo, ACS Catal. 2018, 8, 7445-7454.
[42]	I. A. W. Filot, R.A. van Santen, E. J. M. Hensen, Angew. Chem. Int. Ed. 2014, 53, 12746-12750.
[43]	I. A. Filot, R. J. Broos, J. P. van Rijn, G. J. van Heugten, R. A. van Santen, E. J. Hensen, ACS Catal. 2015, 5, 5453-5467.
[44]	P. W. Atkins, J. De Paula, Atkins' Physical Chemistry, Oxford University Press: Oxford, 2014.
[45]	T. Burdyny, W. A. Smith, Energy Environ. Sci. 2019, 12, 1442-1453.
[46]	H. Ooka, M. C. Figueiredo, M. T. M. Koper, Langmuir, 2017, 33, 9307-9313.
[47]	M. Auinger, I. Katsounaros, J. C. Meier, S. O. Klemm, P. U. Biedermann, A. A. Topalov, M. Rohwerder, K. J. J. Mayrhofer, Phys. Chem. Chem. Phys. 2011, 13, 16384-16394.
[48]	B. Zijlstra, X. Zhang, J. X. Liu, I. A. W. Filot, Z. Zhou, S. Sun, E. J. M. Hensen, Electrochim Acta. 2020, 335, 135665.
[49]	J. J. Carroll, J. D. Slupsky, A. E. Mather, J. Phys. Chem. Ref. Data. 1991, 20, 1201-1209.
[50]	J. Huang, V. Climent, A. Groβ, J. M. Feliu, Chin. J. Catal. 2022, 43, 2837-2849.
[51]	X. Zhao, Z. H. Levell, S. Yu, Y. Liu, Chem. Rev. 2022, 122, 10675-10709.
[52]	C. Stegelmann, A. Andreasen, C. T. Campbell, J. Am. Chem. Soc. 2009, 131, 8077-8082.
[53]	J. S. Yoo, R. Christensen, T. Vegge, J. K. Nørskov, F. Studt, ChemSusChem, 2016, 9, 358-363.
[54]	Z. Li, A. Cao, Q. Zheng, Y. Fu, T. Wang, K. T. Arul, J.-L. Chen, B. Yang, N. M. Adli, L. Lei, C.-L. Dong, J. Xiao, G. Wu, Y. Hou, Adv. Mater. 2021, 33, 2005113.
[55]	T. Zheng, C. Liu, C. Guo, M. Zhang, X. Li, Q. Jiang, W. Xue, H. Li, A. Li, C.-W. Pao, J. Xiao, C. Xia, J. Zeng, Nat. Nanotechnol. 2021, 16, 1386-1393.
[56]	Y. Shi, Y. Ji, J. Long, Y. Liang, Y. Liu, Y. Yu, J. Xiao, B. Zhang, Nat. Commun. 2020, 11, 3415.
[57]	Z. Yang, F. E. Oropeza, K. H. L. Zhang, APL Mater. 2020, 8, 060901.
[58]	K. Chan, C. Tsai, H. A. Hansen, J. K. Nørskov, ChemCatChem, 2014, 6, 1899-1905.
[59]	J. K. Nørskov, T. Bligaard, A. Logadottir, S. Bahn, L. B. Hansen, M. Bollinger, H. Bengaard, B. Hammer, Z. Sljivancanin, M. Mavrikakis, Y. Xu, S. Dahl, C. J. H. Jacobsen, J. Catal. 2002, 209, 275-278
[60]	A. Ruban, B. Hammer, P. Stoltze, H. L. Skriver, J. K. Nørskov, J. Mol. Catal. A, 1997, 115, 421-429.
[61]	C. Shi, H. A. Hansen, A. C. Lausche, J. K. Nørskov, Phys. Chem. Chem. Phys. 2014, 16, 4720-4727.
[62]	T. Bligaard, J. K. Nørskov, S. Dahl, J. Matthiesen, C. H. Christensen, J. Sehested, J. Catal. 2004, 224, 206-217.
[63]	S. Wang, B. Temel, J. Shen, G. Jones, L. C. Grabow, F. Studt, T. Bligaard, F. Abild-Pedersen, C. H. Christensen, J. K. Nørskov, Catal. Lett. 2011, 141, 370-373.
[64]	T. Jiang, D. J. Mowbray, S. Dobrin, H. Falsig, B. Hvolbœk, T. Bligaard, J. K. Nørskov, J. Phys. Chem. C, 2009, 113, 10548-10553.
[65]	J. K. Nørskov, T. Bligaard, J. Rossmeisl, C. H. Christensen, Nat. Chem. 2009, 1, 37-46.
[66]	R. A. V. Santen, M. Neurock, S. G. Shetty, Chem. Rev. 2010, 110, 2005-2048.
[67]	X. Zong, D. G. Vlachos, J. Chem. Inf. Model. 2022, 62, 4361-4368.
[68]	B. Kumar, V. Atla, J. P. Brian, S. Kumari, T. Q. Nguyen, M. Sunkara, J. M. Spurgeon, Angew. Chem. Int. Ed. 2017, 56, 3645-3649.
[69]	Z. W. She, J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K. Nørskov, T. F. Jaramillo, Science, 2017, 355, aad4998.
[70]	J. K. Nørskov, F. Abild-Pedersen, F. Studt, T. Bligaard, Proc. Natl. Acad. Sci. U. S. A. 2011, 108, 937-943.
[71]	A. H. Motagamwala, J. A. Dumesic, Chem. Rev. 2021, 121, 1049-1076.
[72]	H. A. Hansen, V. Viswanathan, J. K. NØrskov, J. Phys. Chem. C, 2014, 118, 6706-6718.

A computational study of electrochemical CO₂ reduction to formic acid on metal-doped SnO₂

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