Why the abnormal phenomena of D-band center theory exist? A new BASED theory for surface catalysis and chemistry

doi:10.1016/S1872-2067(24)60100-2

Abstract

Abstract:

Since the D-band center theory was proposed, it has been widely used in the fields of surface chemistry by almost all researchers, due to its easy understanding, convenient operation and relative accuracy. However, with the continuous development of material systems and modification strategies, researchers have gradually found that D-band center theory is usually effective for large metal particle systems, but for small metal particle systems or semiconductors, such as single atom systems, the opposite conclusion to the D-band center theory is often obtained. To solve the issue above, here we propose a bonding and anti-bonding orbitals stable electron intensity difference (BASED) theory for surface chemistry. The newly-proposed BASED theory can not only successfully explain the abnormal phenomena of D-band center theory, but also exhibits a higher accuracy for prediction of adsorption energy and bond length of intermediates on active sites. Importantly, a new phenomenon of the spin transition state in the adsorption process is observed based on the BASED theory, where the active center atom usually yields an unstable high spin transition state to enhance its adsorption capability in the adsorption process of intermediates when their distance is about 2.5 Å. In short, the BASED theory can be considered as a general principle to understand catalytic mechanism of intermediates on surfaces.

Key words: Surface chemistry, Surface catalysis, D-band center theory, Bonding orbital, Anti-bonding orbital

Zelong Qiao, Run Jiang, Jimmy Yun, Dapeng Cao. Why the abnormal phenomena of D-band center theory exist? A new BASED theory for surface catalysis and chemistry[J]. Chinese Journal of Catalysis, 2024, 64: 44-53.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60100-2

https://www.cjcatal.com/EN/Y2024/V64/I9/44

Figures/Tables 5

Fig. 1. Illustrations of D-band center theory and anti-D-band center phenomenon. (a) D-band center theory; (b) Anti-D-band center phenomenon.

Fig. 2. Illustrations of BASED theory. (a) Schematic diagram of molecular orbital conversion to BASED. (b?d) Schematic diagram of three different bonding and anti-bonding orbitals, where the anti-bonding orbitals gradually right shift until they become unoccupied orbitals.

Fig. 3. Adsorption illustrations of different surface models. (a) The O*, OH*, H*, CH3* and NH2* adsorption models of SAC, including all kinds of 3d transition metal SACs. (b) The O*, OH*, OOH* and H* adsorption models of expanded material surface models (Bulk models) after adsorption, including RuO2 (001), Pt (111), Ni (111), Ag (111), and Cu (111) bulk models.

Fig. 4. Theoretical calculation results from different methods. The relationship between adsorption energy of intermediates and εd, OH* (a), O* (b) and H* (c). (d) The red circle represents four types of SACs with anti-D-band center phenomenon. (e) Projected DOS (PDOS) diagram of all 3d metal SACs slab. (f) The relationship between -ICOHP and adsorption energy. The larger the -ICOHP, the stronger the adsorption capability. The relationship between Q and adsorption energy. The larger the Q, the stronger the adsorption capability. (g) The relationship between -ICOHP and bond length. (h) The relationship between Q and bond length.

Fig. 5. Illustrations of STS phenomenon. (a) Schematic diagram of active center atoms in low spin state. (b) Schematic diagram of active center atoms in high spin state. (c) Schematic diagram of active center atoms completing adsorption process. The relationship between magnetic moment of active center atoms and the distance between the adsorbent (H*, O* and OH*) and slab, based on FeN4 (d), CoN4 (e), NiN4 (f), where the gray arrow represents the trend of magnetic moment variation with height. The relationship between magnetic moment of active center atoms and Q, based on FeN4 (g), CoN4 (h), NiN4 (i). High value of Q represents strong adsorption capability of the active center atom. The gray arrow represents the trend of the adsorption capability indicator Q with respect to magnetic moment.

References

[1]	P. Li, Y. L. Jiang, Y. C. Hu, Y. N. Men, Y. W. Liu, W. B. Cai, S. L. Chen, Nat. Catal., 2022, 5, 900-911.
[2]	X. Li, Z. Huang, C. E. Shuck, G. Liang, Y. Gogotsi, C. Zhi, Nat. Rev. Chem., 2022, 6, 389-404.
[3]	Z.-Y. Wu, F.-Y. Chen, B. Li, S.-W. Yu, Y. Z. Finfrock, D. M. Meira, Q.-Q. Yan, P. Zhu, M.-X. Chen, T.-W. Song, Z. Yin, H.-W. Liang, S. Zhang, G. Wang, H. Wang, Nat. Mater., 2023, 22, 100-108.
[4]	Y. Luo, Z. Zhang, M. Chhowalla, B. Liu, Adv. Mater., 2022, 34, 2108133.
[5]	Z. Niu, Z. Lu, Z. L. Qiao, S. T. Wang, X. Cao, X. D. Chen, J. Yun, L. R. Zheng, D. P. Cao, Adv. Mater., 2024, 36, 2310690.
[6]	T. Pu, W. Zhang, M. Zhu, Angew. Chem. Int. Ed., 2023, 62, e202212278.
[7]	Y. B. Qi, Y. Zhang, L. Yang, Y. H. Zhao, Y. H. Zhu, H. L. Jiang, C. Z. Li, Nat. Commun., 2022, 13, 4602.
[8]	J. X. Guo, Y. Zheng, Z. P. Hu, C. Y. Zheng, J. Mao, K. Du, M. Jaroniec, S. Z. Qiao, T. Ling, Nat. Energy, 2023, 8, 264-272.
[9]	P. Sun, Z. Qiao, X. Dong, R. Jiang, Z. T. Hu, J. Yun, D. Cao, J. Am. Chem. Soc., 2024, 146, 15515-15524.
[10]	X. Ding, R. Jiang, J. Wu, M. Xing, Z.L. Qiao, X. Zeng, S. T. Wang, D. P. Cao, Adv. Funct. Mater., 2023, 33, 2306786.
[11]	A. Gross, S. Sakong, Chem. Rev., 2022, 122, 10746-10776.
[12]	X. X. Wei, B. Zhang, B. Wu, Y. J. Wang, X. H. Tian, L. X. Yang, E. E. Oguzie, X. L. Ma, Nat. Commun., 2022, 13, 726.
[13]	B. Zhang, Q. Zhu, C. Xu, C. Li, Y. Ma, Z. Ma, S. Liu, R. Shao, Y. Xu, B. Jiang, L. Gao, X. Pang, Y. He, G. Chen, L. Qiao, Nat. Commun., 2022, 13, 3858.
[14]	X. Kang, F. Yang, Z. Zhang, H. Liu, S. Ge, S. Hu, S. Li, Y. Luo, Q. Yu, Z. Liu, Q. Wang, W. Ren, C. Sun, H.-M. Cheng, B. Liu, Nat. Commun., 2023, 14, 3607.
[15]	E. Perez-Botella, S. Valencia, F. Rey, Chem. Rev., 2022, 122, 17647-17695.
[16]	C. Wu, X. Wang, Y. Tang, H. Zhong, X. Zhang, A. Zou, J. Zhu, C. Diao, S. Xi, J. Xue, J. Wu, Angew. Chem. Int. Ed., 2023, 62, e202218599.
[17]	H. X. Xu, D. Cheng, D. P. Cao, X. C. Zeng, Nat. Catal., 2024, 7, 207-218.
[18]	H. X. Xu, D. Cheng, D. P. Cao, X. C. Zeng, Nat. Catal., 2018, 1, 339-348.
[19]	B. Hammer, J. K. Nørskov, Surf. Sci., 1995, 343, 211-220.
[20]	B. Hammer, J. K. Norskov, Nature, 1995, 376, 238-240.
[21]	B. Hammer, J. K. Nørskov, Adv. Catal., 2000, 45, 71-129.
[22]	J. K. Norskov, F. Abild-Pedersen, F. Studt, T. Bligaard, Proc. Natl. Acad. Sci. U. S. A., 2011, 108, 937-943.
[23]	J. K. Nørskov, F. Studt, F. Abild-Pedersen, T. Bligaard, in: Fundamental Concepts in Heterogeneous Catalysis, John Wiley & Sons, Inc., 2014, 114-137.
[24]	Z. Hou, C. Cui, Y. Li, Y. Gao, D. Zhu, Y. Gu, G. Pan, Y. Zhu, T. Zhang, Adv. Mater., 2023, 35, 2209876.
[25]	Z. Y. Xiao, P. P. Sun, Z. L. Qiao, K. W. Qiao, H. X. Xu, S. T. Wang, D. P. Cao, Chem. Eng. J., 2022, 446, 137112.
[26]	S. Q. Huang, Z. L. Qiao, P. P. Sun, K. W. Qiao, K. Pei, L. Yang, H. X. Xu, S. T. Wang, Y. Huang, Y. S. Yan, D. P. Cao, Appl. Catal. B, 2022, 317, 121770.
[27]	T. H. Yu, T. Hofmann, Y. Sha, B. V. Merinov, D. J. Myers, C. Heske, W. A. Goddard III, J. Phys. Chem. C, 2013, 117, 26598-26607.
[28]	A. Vojvodic, J. K. Norskov, F. Abild-Pedersen, Top. Catal., 2014, 57, 25-32.
[29]	S. Saini, J. Halldin Stenlid, F. Abild-Pedersen, npj Comput. Mater., 2022, 8, 163.
[30]	D. Wu, K. Kusada, Y. Nanba, M. Koyama, T. Yamamoto, T. Toriyama, S. Matsumura, O. Seo, I. Gueye, J. Kim, L. S. R. Kumara, O. Sakata, S. Kawaguchi, Y. Kubota, H. Kitagawa, J. Am. Chem. Soc., 2022, 144, 3365-3369.
[31]	Y. Nanba, M. Koyama, J. Phys. Chem. C, 2019, 123, 28114-28122.
[32]	M. Li, Z. Li, X. Yu, Y. Wu, C. Mo, M. Luo, L. Li, S. Zhou, Q. Liu, N. Wang, K. L. Yeung, S. Chen, Chem. Eng. J., 2022, 431, 133339.
[33]	Y. Wang, W. Cheng, P. Yuan, G. Yang, S. Mu, J. Liang, H. Xia, K. Guo, M. Liu, S. Zhao, G. Qu, B.-A. Lu, Y. Hu, J. Hu, J.-N. Zhang, Adv. Sci., 2021, 8, 2102915.
[34]	Z. Duan, G. Henkelman, ACS Catal., 2020, 10, 12148-12155.
[35]	L. Zhao, J. H. Yan, H. J. Huang, X. Du, H. Chen, X. He, W. X. Li, W. Fang, D. H. Wang, X. H. Zeng, J. C. Dong, Y. Q. Liu, Adv. Funct. Mater., 2023, 34, 2310902.
[36]	D. M. Janas, A. Droghetti, S. Ponzoni, I. Cojocariu, M. Jugovac, V. Feyer, M. M. Radonjic, I. Rungger, L. Chioncel, G. Zamborlini, M. Cinchetti, Adv. Mater., 2023, 35, 2205698.
[37]	K. Liu, J. Fu, Y. Lin, T. Luo, G. Ni, H. Li, Z. Lin, M. Liu, Nat. Commun., 2022, 13, 2075.
[38]	R. Jiang, Z. L. Qiao, H. X. Xu, D. P. Cao, Chin. J. Catal., 2023, 48, 224-234.
[39]	R. Jiang, Z. Qiao, H. Xu, D. Cao, Nanoscale, 2023, 15, 16775-16783.
[40]	H. Liu, J. Gao, X. Xu, Q. Jia, L. Yang, S. T. Wang, D. P. Cao, Chem. Eng. J., 2022, 448, 137706.
[41]	Z. X. Song, X. Chi, S. Dong, B. Meng, X. J. Yu, X. L. Liu, Y. Zhou, J. Wang, Angew. Chem. Int. Ed., 2024, 63, e202317267.
[42]	X. F. Yang, A. Wang, B. Qiao, J. Li, J. Liu, T. Zhang, Acc. Chem. Res, 2013, 46, 1740-1748.
[43]	Z. Y. Jin, P. P. Li, Y. Meng, Z. W. Fang, D. Xiao, G. H. Yu, Nat. Catal., 2021, 4, 615-622.
[44]	L. Yang, D. Cheng, H. X. Xu, X. Zeng, X. Wan, J. Shui, Z. Xiang, D. P. Cao, Proc. Natl. Acad. Sci. U. S. A., 2018, 115, 6626-6631.
[45]	L. Yang, L. Shi, D. Wang, Y. Lv, D. P. Cao, Nano Energy, 2018, 50, 691-698.
[46]	J. Zhang, X. Xu, L. Yang, D. Cheng, D. P. Cao, Small Methods, 2019, 3, 1900653.
[47]	Z. Qiao, R. Jiang, H. Xu, D. Cao, X. C. Zeng, Angew. Chem. Int. Ed., 2024, 63, e202407812.
[48]	G. Kresse, J. Furthmüller, Comput. Mater. Sci, 1996, 6, 15-50.
[49]	K. Mathew, R. Sundararaman, K. Letchworth-Weaver, T.A. Arias, R.G. Hennig, J. Chem. Phys., 2014, 140, 084106.
[50]	R. Nelson, C. Ertural, J. George, V.L. Deringer, G. Hautier, R. Dronskowski, J. Comput. Chem., 2020, 41, 1931-1940.
[51]	V. L. Deringer, A.L. Tchougreeff, R. Dronskowski, J. Phys. Chem. A, 2011, 115, 5461-5466.
[52]	P. Sun, Z. Qiao, S. Wang, D. Li, X. Liu, Q. Zhang, L. Zheng, Z. Zhuang, D. Cao, Angew. Chem. Int. Ed., 2023, 62, e202216041.
[53]	J. Hwang, R. R. Rao, L. Giordano, Y. Katayama, Y. Yu, Y. Shao-Horn, Science, 2017, 358, 751-756.
[54]	X. J. Xin, C. S. Guo, R. Pang, X. Q. Shi, Y. Zhao, Appl. Surf. Sci., 2021, 570, 151126.
[55]	Y. Sun, S. Sun, H. Yang, S. Xi, J. Gracia, Z. J. Xu, Adv. Mater., 2020, 32, 2003297.
[56]	X. Q. Wei, S. J. Song, W. W. Cai, X. Luo, L. Jiao, Q. Fang, X. S. Wang, N. N. Wu, Z. Luo, H. J. Wang, Z. H. Zhu, J. Li, L. R. Zheng, W. L. Gu, W. Y. Song, S. J. Guo, C. Z. Zhu, Chem, 2023, 9, 181-197.
[57]	C. Chen, W. Chen, Q. Liu, Y. Liu, G. Xiao, C. Chen, F. Li, J. Zhou, ACS Appl. Nano Mater., 2022, 5 12646-12655.
[58]	G. Feng, M. Gao, L. Wang, J. Chen, M. Hou, Q. Wan, Y. Lin, G. Xu, X. Qi, S. Chen, Nat. Commun., 2022, 13, 2652.
[59]	G. Wu, X. Han, J. Cai, P. Yin, P. Cui, X. Zheng, H. Li, C. Chen, G. Wang, X. Hong, Nat. Commun., 2022, 13, 4200.
[60]	Z. Chen, J. Wang, M. Hao, Y. Xie, X. Liu, H. Yang, G. I. N. Waterhouse, X. Wang, S. Ma, Nat. Commun., 2023, 14, 1106.
[61]	S. Maintz, V. L. Deringer, A. L. Tchougreeff, R. Dronskowski, J. Comput. Chem., 2016, 37, 1030-1035.
[62]	S. Maintz, V. L. Deringer, A. L. Tchougreeff, R. Dronskowski, J. Comput. Chem., 2013, 34, 2557-2567.
[63]	X. Ma, H. Xin, Phys. Rev. Lett., 2017, 118, 036101.
[64]	A. Ruban, B. Hammer, P. Stoltze, H. L. Skriver, J. K. Nørskov, J. Mol. Catal. A, 1997, 115, 421-429.
[65]	R. Qi, B. Zhu, Z. Han, Y. Gao, ACS Catal., 2022, 12, 8269-8278.
[66]	A. Allangawi, N. Kosar, K. Ayub, M. A. Gilani, N. H. B. Zainal Arfan, M. H. S. A. Hamid, M. Imran, N. S. Sheikh, T. Mahmood, ACS Omega, 2023, 8, 37820-37829.