Charge transfer and orbital reconstruction of non-noble transition metal single-atoms anchored on Ti2CTx-MXenes for highly selective CO2 electrochemical reduction

doi:10.1016/S1872-2067(21)64018-4

Abstract

Abstract:

Inspired by MXene nanosheets and their regulation of surface functional groups, a series of Ti₂C-based single-atom electrocatalysts (TM@Ti₂CT_x, TM = V, Cr, Mn, Fe, Co, and Ni) with two different functional groups (T = -O and -S) was designed. The CO₂RR catalytic performance was studied using well-defined ab initio calculations. Our results show that the CO₂ molecule can be more readily activated on TM @Ti₂CO₂ than the TM@Ti₂CS₂surface. Bader charge analysis reveals that the Ti₂CO₂ substrate is involved in the adsorption reaction, and enough electrons are injected into the 2π*_u orbital of CO₂, leading to a V-shaped CO₂ molecular configuration and partial negative charge distribution. The V-shaped CO₂ further reduces the difficulty of the first hydrogenation reaction step. The calculated ΔG of the first hydrogenation reaction on TM@Ti₂CO₂ was significantly lower than that of the TM@Ti₂CS₂ counterpart. However, the subsequent CO₂ reduction pathways show that the U_L of the potential determining step on TM@Ti₂CS₂ is smaller than that of TM@Ti₂CO₂. Combining the advantages of both TM@Ti₂CS₂ and TM@Ti₂CO₂, we designed a mixed functional group surface with -O and -S to anchor TM atoms. The results show that Cr atoms anchored on the surface of mixed functional groups exhibit high catalytic activity for the selective production of CH₄. This study opens an exciting new avenue for the rational design of highly selective MXene-based single-atom CO₂RR electrocatalysts.

Key words: TM@Ti₂CT_x MXene, Single-atom catalyst, CO₂RR, Orbital reconstruction, Charge transform, Mixed functional group surface

Neng Li, Jiahe Peng, Zuhao Shi, Peng Zhang, Xin Li. Charge transfer and orbital reconstruction of non-noble transition metal single-atoms anchored on Ti₂CT_x-MXenes for highly selective CO₂ electrochemical reduction[J]. Chinese Journal of Catalysis, 2022, 43(7): 1906-1917.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)64018-4

https://www.cjcatal.com/EN/Y2022/V43/I7/1906

Figures/Tables 12

Fig. 1. Optimized models of Ti2CO2 (a) and Ti2CS2 (b) (color scheme: Ti, cyan; C, brown; O, red; S, yellow). Circles represent the possible sites of TM on Ti2CTx. Calculated DOS of Ti2CO2 (c) and Ti2CS2 (d). Fermi energy level is set to zero.

Fig. 2. (a) Top view of three adsorption configurations (H1, H2, and T1 sites) of TM atoms on Ti2CO2 and Ti2CS2. (b) Side view of the TM adsorption configurations at Ti2CTx H1 sites. (c) Binding energies of transition metal atoms on Ti2CO2 and Ti2CS2.

Fig. 3. (a) Optimized geometric structures of CO2 adsorbed on TM@Ti2CO2 and TM@Ti2CS2. (b) Possible chemisorption path for the interaction of CO2 with TM@Ti2CTx surfaces. (c) Process of CO2 adsorption with a V-shaped configuration from linear CO2 in the gas phase with the inclusion of transition state calculation.

Table 1 Binding energy (BE), binding distance (BD), and bond angle (BA) of CO2 adsorbed on TM@Ti2CO2 and TM@Ti2CS2 in the most stable configuration.

Metal	Ti₂CO₂			Ti₂CS₂
Metal	BE (eV)	BD (TM-O, Å)	BA (∠OCO, °)	BE (eV)	BD (TM-O, Å)	BA (∠OCO, °)
V	-0.3104	1.97	142.1	-0.5682	2.20	177.4
Cr	-0.6850	1.99	146.7	-0.5015	2.21	177.0
Mn	-0.4306	1.96	144.9	-0.4784	2.25	178.8
Fe	-0.4966	1.99	151.2	-0.3923	2.21	179.2
Co	-0.3250	1.99	150.4	-0.1630	2.45	179.9
Ni	-0.2074	1.98	154.7	-0.2258	2.46	179.9

Fig. 4. PDOS of C and O orbitals of CO2 as well as the 3d orbital of Cr in Cr@Ti2CO2 before (a) and after (c) adsorption; PDOS of C and O orbitals of CO2 and the 3d orbital of Cr in Cr@Ti2CS2 before (b) and after (d) adsorption. (e) Bader differences of C and O atoms in CO2 adsorbed on TM@Ti2CO2 and TM@Ti2CS2. (f) Bader charge difference of Ti2CO2, Ti2CS2, and TM anchored on Ti2CTx. (g) Bader charge difference of O or S atoms on the upper surface side. (h) Gibbs free energy changes of the first hydrogenation reactions on TM@Ti2CO2 and TM@Ti2CS2.

Fig. 5. Schematic diagram of CO2 activation mechanism on TM/Ti2CTx.

Fig. 6. DFT-optimized adsorption structures and the free energy diagrams for the elementary hydrogenation steps of CO2 reduction on V@Ti2CO2 (a), Cr@Ti2CO2 (b), Mn@Ti2CO2 (c), Fe@Ti2CO2 (d), Co@Ti2CO2 (e), and Ni@Ti2CO2 (f). Only the minimum energy pathways are shown.

Fig. 7. DFT-optimized adsorption structures and the free energy diagrams for the elementary hydrogenation steps of CO2 reduction on V@Ti2CS2 (a), Cr@Ti2CS2 (b), Mn@Ti2CS2 (c), Fe@Ti2CS2 (d), Co@Ti2CS2 (e), and Ni@Ti2CS2 (f). Only the minimum energy pathways are shown.

Table 2 DFT-predicted potential determining steps (PDSs), UL values, and possible product on TM@Ti2CO2 and TM@Ti2CS2.

Catalyst	PDS	U_L (V)	Production
V@Ti₂CO₂	OH + H⁺ + e^- → H₂O	0.57	CH₄
Cr@Ti₂CO₂	CO + H⁺+ e^- → CHO	0.53	CH₄
Mn@Ti₂CO₂	HCOOH + H⁺+ e^- → CH₂OOH	0.41	CH₄
Fe@Ti₂CO₂	HCOOH + H⁺+ e^- → CHO + H₂O	0.54	CH₄
Co@Ti₂CO₂	CO → CO +	0.70	CO
Ni@Ti₂CO₂	CO → CO +	0.48	CO
V@Ti₂CS₂	OH + H⁺ + e^- → H₂O	0.74	CH₄
Cr@Ti₂CS₂	HCOO + H⁺+ e^- → HCOOH	0.15	CH₄
Mn@Ti₂CS₂	HCOO + H⁺+ e^- → HCOOH	0.18	CH₄
Fe@Ti₂CS₂	HCOOH + H⁺+ e^- → CH₂OOH	0.17	CH₄
Co@Ti₂CS₂	CO₂ + H⁺+ e^- → OCHO	0.18	HCOOH
Ni@Ti₂CS₂	CO₂ + H⁺+ e^- → COOH	0.71	HCOOH

Fig. 8. Free energy diagrams of CO2RR on Co@Ti2CS2 (a), Fe@Ti2CS2 (b), Mn@Ti2CS2 (c), and Cr@Ti2CS2 (d) with inclusion solvation effect.

Fig. 9. Optimized models of Cr@OOS (a) and CO2 adsorbed on Cr@OOS (b). Top panel provides the vertical view, and the bottom panel presents the side view. (c) DFT-optimized adsorption structures and the free energy diagrams for the elementary hydrogenation steps of CO2 reduction on Cr@OOS. (d) Free energy diagrams of CO2RR on Cr@OOS with the inclusion of the solvation effect. (e) UL of CO2RR on Cr@OOS vs. HER.

Fig. 10. (a) Energy and temperature fluctuations of Cr@OOS within 10 ps in AIMD simulations at 330 K. (b) Calculated Pourbaix diagram of Cr@OOS. Gray dashed lines are the water redox potentials.

References

[1]	L. Wang, W. Chen, D. Zhang, Y. Du, R. Amal, S. Qiao, J. Wu, Z. Yin, Chem. Soc. Rev., 2019, 48, 5310-5349.
[2]	X. Li, J. Yu, M. Jaroniec, X. Chen, Chem. Rev., 2019, 119, 3962-4179.
[3]	M. M. Ayyub, C. N. R. Rao, Mater. Horiz., 2021, 8, 2420-2443.
[4]	S. Gao, Y. Lin, X. Jiao, Y. Sun, Q. Luo, W. Zhang, D. Li, J. Yang, Y. Xie, Nature, 2016, 529, 68-71.
[5]	C.-T. Dinh, T. Burdyny, M. G. Kibria, A. Seifitokaldani, C. M. Gabardo, F. P. García de Arquer, A. Kiani, J. P. Edwards, P. De Luna, O. S. Bushuyev, C. Zou, R. Quintero-Bermudez, Y. Pang, D. Sinton, E. H. Sargent, Science, 2018, 360, 783-787.
[6]	X. Li, J. Wen, J. Low, Y. Fang, J. Yu, Sci. China Mater., 2014, 57, 70-100.
[7]	Y. Zhou, F. Che, M. Liu, C. Zou, Z. Liang, P. De Luna, H. Yuan, J. Li, Z. Wang, H. Xie, H. Li, P. Chen, E. Bladt, R. Quintero-Bermudez, T.-K. Sham, S. Bals, J. Hofkens, D. Sinton, G. Chen, E. H. Sargent, Nat. Chem., 2018, 10, 974-980.
[8]	A. S. Varela, N. Ranjbar Sahraie, J. Steinberg, W. Ju, H.-S. Oh, P. Strasser, Angew. Chem. Int. Ed., 2015, 54, 10758-10762.
[9]	A. A. Peterson, F. Abild-Pedersen, F. Studt, J. Rossmeisl, J. K. Nørskov, Energy Environ. Sci., 2010, 3, 1311-1315.
[10]	Y. Hori, H. Wakebe, T. Tsukamoto, O. Koga, Electrochim. Acta, 1994, 39, 1833-1839.
[11]	Y. Hori, A. Murata, R. Takahashi, J. Chem. Soc., Faraday Trans. 1, 1989, 85, 2309-2326.
[12]	X. Li, L. Liu, X. Ren, J. Gao, Y. Huang, B. Liu, Sci. Adv., 2020, 6, eabb6833.
[13]	T. N. Nguyen, M. Salehi, Q. V. Le, A. Seifitokaldani, C. T. Dinh, ACS Catal., 2020, 10, 10068-10095.
[14]	X. Cui, W. An, X. Liu, H. Wang, Y. Men, J. Wang, Nanoscale, 2018, 10, 15262-15272.
[15]	M. Li, H. Wang, W. Luo, P. C. Sherrell, J. Chen, J. Yang, Adv. Mater., 2020, 32, 2001848.
[16]	Y. Wang, J. Mao, X. Meng, L. Yu, D. Deng, X. Bao, Chem. Rev., 2019, 119, 1806-1854.
[17]	S. K. Kaiser, Z. Chen, D. Faust Akl, S. Mitchell, J. Pérez-Ramírez, Chem. Rev., 2020, 120, 11703-11809.
[18]	J. Peng, X. Chen, W.-J. Ong, X. Zhao, N. Li, Chem, 2019, 5, 18-50.
[19]	N. Li, J. Peng, W.-J. Ong, T. Ma, Arramel, P. Zhang, J. Jiang, X. Yuan, C. Zhang, Matter, 2021, 4, 377-407.
[20]	D. Zhao, Z. Chen, W. Yang, S. Liu, X. Zhang, Y. Yu, W.-C. Cheong, L. Zheng, F. Ren, G. Ying, X. Cao, D. Wang, Q. Peng, G. Wang, C. Chen, J. Am. Chem. Soc., 2019, 141, 4086-4093.
[21]	J. Zhang, Y. Zhao, X. Guo, C. Chen, C.-L. Dong, R.-S. Liu, C.-P. Han, Y. Li, Y. Gogotsi, G. Wang, Nat. Catal., 2018, 1, 985-992.
[22]	H. Song, R. Du, Y. Wang, D. Zu, R. Zhou, Y. Cai, F. Wang, Z. Li, Y. Shen, C. Li, Appl. Catal. B, 2021, 286, 119898.
[23]	M. Zhang, C. Lai, B. Li, S. Liu, D. Huang, F. Xu, X. Liu, L. Qin, Y. Fu, L. Li, H. Yi, L. Chen, Small, 2021, 17, 2007113.
[24]	J. Qu, J. Xiao, H. Chen, X. Liu, T. Wang, Q. Zhang, Chin. J. Catal., 2021, 42, 288-296.
[25]	Z. Deng, X. Zheng, M. Deng, L. Li, L. Jing, Z. Wei, Chin. J. Catal., 2021, 42, 1659-1666.
[26]	D. A. Kuznetsov, Z. Chen, P. V. Kumar, A. Tsoukalou, A. Kierzkowska, P. M. Abdala, O. V. Safonova, A. Fedorov, C. R. Müller, J. Am. Chem. Soc., 2019, 141, 17809-17816.
[27]	W. Peng, M. Luo, X. Xu, K. Jiang, M. Peng, D. Chen, T.-S. Chan, Y. Tan, Adv. Energy Mater., 2020, 10, 2001364.
[28]	H. Liu, Z. Hu, Q. Liu, P. Sun, Y. Wang, S. Chou, Z. Hu, Z. Zhang, J. Mater. Chem. A, 2020, 8, 24710-24717.
[29]	V. Ramalingam, P. Varadhan, H.-C. Fu, H. Kim, D. Zhang, S. Chen, L. Song, D. Ma, Y. Wang, H. N. Alshareef, J.-H. He, Adv. Mater., 2019, 31, 1903841.
[30]	F. Liu, A. Zhou, J. Chen, J. Jia, W. Zhou, L. Wang, Q. Hu, Appl. Surf. Sci., 2017, 416, 781-789.
[31]	Y. Wang, M. Zhou, L.-C. Xu, W. Zhao, R. Li, Z. Yang, R. Liu, X. Li, J. Power Sources, 2020, 451, 227791.
[32]	Y. Gao, Y. Cao, Y. Gu, H. Zhuo, G. Zhuang, S. Deng, X. Zhong, Z. Wei, J. Chen, X. Pan, J.-G. Wang, Appl. Surf. Sci., 2019, 465, 911-918.
[33]	B. Huang, N. Li, W.-J. Ong, N. Zhou, J. Mater. Chem. A, 2019, 7, 27620-27631.
[34]	G. Gao, A. P. O’Mullane, A. Du, ACS Catal., 2017, 7, 494-500.
[35]	Y. Cheng, J. Dai, Y. Song, Y. Zhang, Nanoscale, 2019, 11, 18132-18141.
[36]	V. Kamysbayev, A. S. Filatov, H. Hu, X. Rui, F. Lagunas, D. Wang, R. F. Klie, D. V. Talapin, Science, 2020, 369, 979-983.
[37]	Y. Xiao, W. Zhang, Nanoscale, 2020, 12, 7660-7673.
[38]	Z. Guo, Y. Li, B. Sa, Y. Fang, J. Lin, Y. Huang, C. Tang, J. Zhou, N. Miao, Z. Sun, Appl. Surf. Sci., 2020, 521, 146436.
[39]	N. Li, X. Chen, W.-J. Ong, D. R. MacFarlane, X. Zhao, A. K. Cheetham, C. Sun, ACS Nano, 2017, 11, 10825-10833.
[40]	J. Hafner, J. Comput. Chem., 2008, 29, 2044-2078.
[41]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[42]	P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[43]	S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys., 2010, 132, 154104.
[44]	E. Sanville, S. D. Kenny, R. Smith, G. Henkelman, J. Comput. Chem., 2007, 28, 899-908.
[45]	K. Momma, F. Izumi, J. Appl. Crystallogr., 2011, 44, 1272-1276.
[46]	G. Henkelman, B. P. Uberuaga, H. Jónsson, J. Chem. Phys., 2000, 113, 9901-9904.
[47]	Q. Zhang, A. Asthagiri, Catal. Today, 2019, 323, 35-43.
[48]	F. Calle-Vallejo, R. F. de Morais, F. Illas, D. Loffreda, P. Sautet, J. Phys. Chem. C, 2019, 123, 5578-5582.
[49]	C. M. Gray, K. Saravanan, G. Wang, J. A. Keith, Mol. Simulat., 2017, 43, 420-427.
[50]	C. Guo, T. Zhang, X. Liang, X. Deng, W. Guo, Z. Wang, X. Lu, C.-M. L. Wu, Appl. Surf. Sci., 2020, 533, 147466.
[51]	C. Ao, W. Zhao, S. Ruan, S. Qian, Y. Liu, L. Wang, L. Zhang, Sustain. Energy Fuels, 2020, 4, 6156-6164.
[52]	J.-Y. Liu, X.-Q. Gong, R. Li, H. Shi, S. B. Cronin, A. N. Alexandrova, ACS Catal., 2020, 10, 4048-4058.
[53]	L. Li, B. Li, Q. Guo, B. Li, J. Phys. Chem. C, 2019, 123, 14501-14507.
[54]	H. Dong, C. Liu, Y. Li, D.-E. Jiang, Nanoscale, 2019, 11, 11351-11359.
[55]	J. K. Nörskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. R. Kitchin, T. Bligaard, H. Jónsson, J. Phys. Chem. B, 2004, 108, 17886-17892.
[56]	F. Calle-Vallejo, J. I. Martínez, J. M. García-Lastra, M. Mogensen, J. Rossmeisl, Angew. Chem. Int. Ed., 2010, 49, 7699-7701.
[57]	Y. Li, H. Su, S. H. Chan, Q. Sun, ACS Catal., 2015, 5, 6658-6664.
[58]	P. Li, J. Zhu, A. D. Handoko, R. Zhang, H. Wang, D. Legut, X. Wen, Z. Fu, Z. W. Seh, Q. Zhang, J. Mater. Chem. A, 2018, 6, 4271-4278.
[59]	A. J. Medford, A. Vojvodic, J. S. Hummelshøj, J. Voss, F. Abild-Pedersen, F. Studt, T. Bligaard, A. Nilsson, J. K. Nörskov, J. Catal., 2015, 328, 36-42.
[60]	X. Hong, K. Chan, C. Tsai, J. K. Nørskov, ACS Catal., 2016, 6, 4428-4437.

Charge transfer and orbital reconstruction of non-noble transition metal single-atoms anchored on Ti₂CT_x-MXenes for highly selective CO₂ electrochemical reduction

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