Bimetallic single-cluster catalysts anchored on graphdiyne for alkaline hydrogen evolution reaction

doi:10.1016/S1872-2067(23)64459-6

Abstract

Abstract:

Pt-based electrocatalysts suffer from high water dissociation barriers that limit their overall hydrogen evolution reaction (HER) activities in alkaline media. Here we predict the bimetallic four-atom single-cluster catalysts (SCCs) M₁A₃ (M as later transition metal and A as early transition metal) with pyramidal structure supported on graphdiyne (GDY) for alkaline HER. Theoretical calculations show that the stable Pt₁Ti₃/GDY SCC delivers high alkaline HER activity via the Volmer-Heyrovsky mechanism. The excellent catalytic performance of Pt₁Ti₃/GDY SCC is attributed to both the low-valent Pt site that renders an optimal hydrogen adsorption free energy (ΔG_*H), and the synergic effect of adjacent Ti sites that leads to a low water dissociation barrier. By screening alternative M₁ in M₁Ti₃/GDY for optimal ΔG_*H and facile water dissociation, we further identify the Ir₁Ti₃/GDY SCC to be a potentially high-performing alkaline HER electrocatalyst at low *OH coverage. Our work provides new insights and guidelines for the rational design of alkaline HER electrocatalysts.

Key words: Alkaline hydrogen evolution reaction, Water dissociation kinetics, Single-cluster catalysis, Pt₁Ti₃/Graphdiyne

Bin Chen, Ya-Fei Jiang, Hai Xiao, Jun Li. Bimetallic single-cluster catalysts anchored on graphdiyne for alkaline hydrogen evolution reaction[J]. Chinese Journal of Catalysis, 2023, 50: 306-313.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64459-6

https://www.cjcatal.com/EN/Y2023/V50/I7/306

Figures/Tables 5

Fig. 1. Optimized structure of the GDY-supported Pt1Ti3 cluster. (a) Top view. (b) Side view. The grey, blue and brown spheres represent Pt, Ti and C, respectively.

Fig. 2. Calculated reaction barriers and free energies of water dissociation (a), and HER free-energy diagram at U = 0 V (vs. RHE) (b) for different materials. For Pt1Ti3/GDY, Gads(*H) = G(*H) - G(*) - G(H2)/2 where H adsorbs on Pt1 atom of Pt1Ti3/GDY with each Ti atom is coordinated by one OH group.

Fig. 3. Free energy diagrams for alkaline HER at U = 0 V (vs. RHE) on Pt1Ti3/GDY and the corresponding changes of charges of Pt atom in Pt1Ti3/GDY. Every step for water adsorption that enclosed in the black dashed box are shown in Fig. S8. Three of six H2O molecules are chemisorbed on the three Ti sites and involved in the Volmer step, while the other three H2O molecules are from the solution and involved in the Heyrovsky step.

Fig. 4. The optimized structures of Pt1Ti3/GDY with *H and *OH (left), and the corresponding charge density difference maps (right). Yellow and cyan iso-surface represents electron accumulation and electron depletion, respectively. (isosurface level at 0.002|e| Bohr?3). The grey, blue, brown, red and light brown spheres represent Pt, Ti, C, O and H, respectively.

Fig. 5. Relationship between d-band center of M atom in M1Ti3/GDY and calculated free energy of *H (a,c), reaction free energy (b,d) of water dissociation on M1Ti3/GDY at U = 0 V (vs. RHE), with (each Ti atom is coordinated by one OH group) and without *OH coverage, respectively. The gray region denotes |ΔG*H| < 0.2 eV. For M1Ti3/GDY with *OH coverage, Gads(*H) = G(*H-3*OH) - G(3*OH) - G(H2)/2. Gr = G(*H-3*OH) - G(2*OH-H2O*). For M1Ti3/GDY without *OH coverage, Gads(*H) = G(*H) - E(*) - G(H2)/2. Gr = G(*H - *OH) - G(H2O*).

References

[1]	A. Magistris, G. Chiodelli, M. Villa, J. Power Sources, 1983, 9, 379-382.
[2]	W. Zhou, J. Jia, J. Lu, L. Yang, D. Hou, G. Li, S. Chen, Nano Energy, 2016, 28, 29-43.
[3]	J. D. Benck, T. R. Hellstern, J. Kibsgaard, P. Chakthranont, T. F. Jaramillo, ACS Catal., 2014, 4, 3957-3971.
[4]	Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K. Nørskov, T. F. Jaramillo, Science, 2017, 355, eaad4998.
[5]	I. Ledezma-Yanez, W. D. Z. Wallace, P. Sebastian-Pascual, V. Climent, J. M. Feliu, M. T. M. Koper, Nat. Energy, 2017, 2, 17031.
[6]	N. M. Markovic, T. J. Schmidt, B. N. Grgur, H. A. Gasteiger, R. J. Behm, P. N. Ross, J. Phys. Chem. B, 1999, 103, 8568-8577.
[7]	Y. Zheng, Y. Jiao, A. Vasileff, S.-Z. Qiao, Angew. Chem. Int. Ed. 2018, 57, 7568-7579.
[8]	B. Qiao, A. Wang, X.-F. Yang, L. F. Allard, Z. Jiang, Y.-T. Cui, J.-Y. Liu, J. Li, T. Zhang, Nat. Chem. 2011, 3, 634-641.
[9]	J.-C. Liu, X.-L. Ma, Y. Li, Y.-G. Wang, H. Xiao, J. Li, Nat. Commun., 2018, 9, 1610.
[10]	X.-L. Ma, J.-C. Liu, H. Xiao, J. Li, J. Am. Chem. Soc. 2018, 140, 46-49.
[11]	J.-C. Liu, H. Xiao, J. Li, J. Am. Chem. Soc. 2020, 142, 7, 3375-3383.
[12]	A. Wang, J. Li, T. Zhang, Nat. Rev. Chem. 2018, 2, 65-81.
[13]	P. Buchwalter, J. Rose, P. Braunstein, Chem. Rev., 2015, 115, 28-126.
[14]	J. H. Montoya, C. Tsai, A. Vojvodic, J. K. Norskov, ChemSusChem, 2015, 8, 2180-2186.
[15]	J. H. Montoya, L. C. Seitz, P. Chakthranont, A. Vojvodic, T. F. Jaramillo, J. K. Norskov, Nat. Mater. 2017, 16, 70-81.
[16]	J. Perez-Ramirez, N. Lopez, Nat. Catal. 2019, 2, 971-976.
[17]	R. Subbaraman, D. Tripkovic, D. Strmcnik, K.-C. Chang, M. Uchimura, A. P. Paulikas, V. Stamenkovic, N. M. Markovic, Science, 2011, 334, 1256-1260.
[18]	S. Zhang, L. Nguyen, J. X. Liang, J. Shan, J. J. Liu, A. I. Frenkel, A. Patlolla, W. Huang, J. Li, F. F. Tao, Nat. Commun., 2015, 6, 7938.
[19]	L. Nguyen, S. Zhang, L. Wang, Y. Li, H. Yoshida, A. Patlolla, S. Takeda, A. I. Frenkel, F. Tao, ACS Catal., 2016, 6, 840-850.
[20]	X.-L. Ma, Y. Yang, L.-M. Xu, H. Xiao, W.-Z. Yao, J. Li, J. Mater. Chem. A, 2022, 10, 6146-6152.
[21]	N. Liu, X.-L. Ma, J. Li, H. Xiao, J. Phys. Chem. C, 2021, 125, 27192-27198.
[22]	G. Li, Y. Li, H. Liu, Y. Guo, Y. Li, D. Zhu, Chem. Commun., 2010, 46, 3256-3258.
[23]	J.-C. Liu, H. Xiao, X.-K. Zhao, N.-N. Zhang, Y. Liu, D.-H. Xing, X. H. Yu, H.-S. Hu, J. Li, CCS Chem., 2023, 5, 152-163.
[24]	J. Zhu, L.-S. Hu, P.-X. Zhao, L. Y. S. Lee, K.-Y. Wong, Chem. Rev. 2020, 120, 851-918.
[25]	L.-L. Lin, W. Zhou, R. Gao, S.-Y. Yao, X. Zhang, W.-Q. Xu, S.-J. Zheng, Z. Jiang, Q.-L. Yu, Y.-W. Li, C. Shi, X.-D. Wen, D. Ma, Nature, 2017, 544, 80-83.
[26]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[27]	G. Kresse, J. Furthmüller, Comput. Mater. Sci. 1996, 6, 15-50.
[28]	G. Kresse, D. Joubert, Phys. Rev. B, 1999, 59, 1758-1775.
[29]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1996, 77, 3865-3868.
[30]	G. Henkelman, B. P. Uberuaga, H. J. Jonsson, J. Chem. Phys. 2000, 113, 9901-9904.
[31]	K. Mathew, R. Sundararaman, K. Letchworthweaver, T. A. Arias, R. G. Hennig, J. Chem. Phys. 2014, 140, 084106.
[32]	M. Long, L. Tang, D. Wang, Y. Li, Z. Shuai, ACS Nano, 2011, 5, 2593-2600.
[33]	D.-H. Xing, C.-Q. Xu, Y.-G. Wang, J. Li, J. Phys. Chem. C, 2019, 123, 10494-10500.
[34]	V. Wang, N. Xu, J.-C. Liu, G. Tang, W.-T. Geng, Comput. Phys. Commun. 2021, 267, 108033.
[35]	H. Xiao, T. Cheng, W. A. Goddard, R. Sundararaman, J. Am. Chem. Soc. 2016, 138, 483-486.
[36]	H. Xiao, T. Cheng, W. A. Goddard, J. Am. Chem. Soc. 2017, 139, 130-136.
[37]	J. K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. R. Kitchin, T. Bligaard, H. Jonsson, J. Phys. Chem. B, 2004, 108, 17886-17892.
[38]	C.-S. Huang, Y.-J. Li, N. Wang, Y.-R. Xue, Z.-C. Zuo, H.-B. Liu, Y.-L. Li, Chem. Rev. 2018, 118, 7744-7803.
[39]	Z. Z. Lin, Carbon, 2016, 108, 343-350.
[40]	X.-Y. Guo, J.-X. Gu, S.-R. Lin, S.-L. Zhang, Z.-F. Chen, S.-P. Huang, J. Am. Chem. Soc. 2020, 142, 5709-5721.
[41]	R. Subbaraman, D. Tripkovic, K. C. Chang, D. Strmcnik, A. P. Paulikas, P. Hirunsit, M. Chan, J. Greeley, V. Stamenkovic, N. M. Markovic, Nat. Mater. 2012, 11, 550-557.
[42]	Q. F. Gong, P. Ding, M. Q. Xu, X. R. Zhu, M. Y. Wang, J. Deng, Q. Ma, N. Han, Y. Zhu, J. Lu, Z. X. Feng, Y. F. Li, W. Zhou, Y. G. Li, Nat. Commun. 2019, 10, 2807.
[43]	S. S. He, F. L. Ni, Y. J. Ji, L. Wang, Y. Z. Wen, H. P. Bai, G. J. Liu, Y. Zhang, Y. Y. Li, B. Zhang, H. S. Peng, Angew. Chem. Int. Ed. 2018, 57, 16114-16119.
[44]	S. Zhang, P. Kang, T. J. Meyer, J. Am. Chem. Soc. 2014, 136, 1734-1737.
[45]	G. B. Wen, B. H. Ren, M. G. Park, J. Yang, H. Z. Dou, Z. Zhang, Y. -P. Deng, Z. Y. Bai, L. Yang, J. Gostick, G. A. Botton, Y. F. Hu, Z. W. Chen, Angew. Chem. Int. Ed. 2020, 59, 12860-12867.
[46]	J. K. Nørskov, T. Bligaard, A. Logadottir, J. R. Kitchin, J. G. Chen, S. Pandelov, U. Stimming, J. Electrochem. Soc. 2005, 152, J23-J26.
[47]	S. Trasatti, J. Electroanal. Chem. Interfacial Electrochem. 1972, 39, 163-184.
[48]	E. Skffllason, V. Tripkovic, M. E. Bjçrketun, S. Gudmundsdlttir, G. Karlberg, J. Rossmeisl, T. Bligaard, H. Jlnsson, J. K. Norskov, J. Phys. Chem. C, 2010, 114, 18182-18197.
[49]	D. Strmcnik, P. P. Lopes, B. Genorio, V. R. Stamenkovic, N. M. Markovic, Nano Energy, 2016, 29, 29-36.
[50]	J. Zheng, W. Sheng, Z. Zhuang, B. Xu, Y. Yan, Sci. Adv. 2016, 2, e1501602.
[51]	J. Durst, A. Siebel, C. Simon, F. Hasche, J. Herranz, H. A. Gasteiger, Energy Environ. Sci. 2014, 7, 2255-2260.
[52]	P. J. Rheinl-nder, J. Herranz, J. Durst, H. A. Gasteiger, J. Electrochem. Soc. 2014, 161, F1448-F1457.
[53]	J. Rossmeisl, K. Chan, E. Skffllason, M. E. Bjcrketun, V. Tripkovic, Catal. Today, 2016, 262, 36-40.
[54]	J. Rossmeisl, K. Chan, R. Ahmed, V. Tripkovic, M. E. Bjorketun, Phys. Chem. Chem. Phys. 2013, 15, 10321-10325.
[55]	Y. Zheng, Y. Jiao, Y. Zhu, L. H. Li, Y. Han, Y. Chen, M. Jaroniec, S. Z. Qiao, J. Am. Chem. Soc. 2016, 138, 16174-16181.
[56]	M. Pozzo, G. Carlini, R. Rosei, D. AlfH, J. Chem. Phys. 2007, 126, 164706.
[57]	G. S. Karlberg, Phys. Rev. B, 2006, 74, 153414.
[58]	S. Meng, E. G. Wang, S. Gao, Phys. Rev. B, 2004, 69, 195404.
[59]	J. Greeley, M. Mavrikakis, Nat. Mater. 2004, 3, 810-815.
[60]	V. R. Stamenkovic, D. Strmcnik, P. P. Lopes, N. M. Markovic, Nat. Mater., 2017, 16, 57-69.
[61]	L. G. Li, P. T. Wang, Q. Shao, X. Q. Huang, Chem. Soc. Rev., 2020, 49, 3072-3106.
[62]	G. Di Liberto, L. A. Cipriano, G. Pacchioni, J. Am. Chem. Soc. 2021, 143, 20431-20441.
[63]	P. J. Feibelman, Science, 2002, 295, 99-102.
[64]	A. Michaelides, P. Hu, J. Am. Chem. Soc. 2001, 123, 4235-4242.
[65]	B. You, X. Liu, G. Hu, S. Gul, J. Yano, D. Jiang, Y. Sun, J. Am. Chem. Soc. 2017, 139, 12283-12290.
[66]	N. Danilovic, R. Subbaraman, D. Strmcnik, K. C. Chang, A. P. Paulikas, V. R. Stamenkovic, N. M. Markovic, Angew. Chem. Int. Ed. 2012, 51, 12495-12498.
[67]	Z. Zeng, K. C. Chang, J. Kubal, N. M. Markovic, J. Greeley, Nat. Energy, 2017, 2, 17070.
[68]	H. Yin, S. Zhao, K. Zhao, A. Muqsit, H. Tang, L. Chang, H. Zhao, Y. Gao, Z. Tang, Nat. Commun. 2015, 6, 6430.
[69]	P. Wang, X. Zhang, J. Zhang, S. Wan, S. Guo, G. Lu, J. Yao, X. Huang, Nat. Commun. 2017, 8, 14580.
[70]	L. Wang, Y. Zhu, Z. Zeng, C. Lin, M. Giroux, L. Jiang, Y. Han, J. Greeley, C. Wang, J. Jin, Nano Energy, 2017, 31, 456-461.
[71]	D. Kobayashi, H. Kobayashi, D. Wu, S. Okazoe, K. Kusada, T. Yamamoto, T. Toriyama, S. Matsumura, S. Kawaguchi, Y. Kubota, S. M. Aspera, H. Nakanishi, S. Arai, H. Kitagawa, J. Am. Chem. Soc., 2020, 142, 17250-17254.
[72]	Q. Q. Yan, D. X. Wu, S. Q. Chu, Z. Q. Chen, Y. Lin, M. X. Chen, J. Zhang, X. J. Wu, H. W. Liang, Nat. Commun., 2019, 10, 4977.
[73]	J. N. Brønsted, Chem. Rev. 1928, 5, 231-338.
[74]	M. G. Evans, M. Polanyi, Trans. Faraday Soc. 1938, 34, 11-24.