Breaking the scaling relations for efficient N2-to-NH3 conversion by a bowl active site design: Insight from LaRuSi and isostructural electrides

doi:10.1016/S1872-2067(22)64129-9

Abstract

Abstract:

The design of optimal heterogeneous catalysts for N₂-to-NH₃ conversion is often dictated by the scaling relations, which result in a volcano curve that poses a limit on the catalytic performance. Herein, we reveal a bowl active site that can break the scaling relations, through investigating the catalytic mechanisms of N₂-to-NH₃ conversion on the lanthanide intermetallic electride catalyst LaRuSi by first-principles modeling. This bowl active site, composed of four surface La cations and one subsurface Si atom rich in electrons, plays the key role in enabling efficient catalysis. With adaptive electrostatic and orbital interactions, the bowl active site promotes the adsorption and activation of N₂ that delivers facile cleavage of N‒N bond, while destabilizes the adsorptions of *NH_x (x = 1, 2, 3) species, which facilitates the release of the final NH₃ product. By comparison with other electride catalysts isostructural to LaRuSi, we confirm the breaking of scaling relations between the adsorptions of *NH_x species and that of *N on the bowl active site. Thus, this bowl active site presents a design concept that breaks the scaling relations for highly efficient heterogeneous catalysis of N₂-to-NH₃ conversion.

Key words: N2-to-NH3 conversion, Scaling relations, Heterogeneous catalyst design, First-principles calculations

Ya-Fei Jiang, Jin-Cheng Liu, Cong-Qiao Xu, Jun Li, Hai Xiao. Breaking the scaling relations for efficient N₂-to-NH₃ conversion by a bowl active site design: Insight from LaRuSi and isostructural electrides[J]. Chinese Journal of Catalysis, 2022, 43(8): 2183-2192.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64129-9

https://www.cjcatal.com/EN/Y2022/V43/I8/2183

Figures/Tables 5

Fig. 1. Electronic structure analyses of the most stable conformation of N2 adsorbed on the LaRuSi(001)-La surface. (a) Charge density difference upon N2 adsorption. (b) The bowl active site with selected bond lengths shown in the unit of ?. (c) Partial electron density in the energy range between Ef and Ef ? 1.0 eV on the (110) plane. (d) Projected densities of states (pDOS) of selected atoms on the LaRuSi(001)-La surface (i) before and (ii) after N2 adsorption. (iii) Crystal orbital Hamilton population (COHP) between the adsorbed N2 and LaRuSi(001)-La surface.

Fig. 2. The Gibbs free energy profiles for catalytic mechanisms of N2-to-NH3 conversion on the LaRuSi(001)-La surface, including all viable branches for both the dissociative and associative mechanisms. The superscripts b and t denote the bridge and top sites, respectively. Structures of intermediates and transition states (TS) along all the pathways are shown in Fig. S6.

Fig. 3 (a) Evolution of Si charge and distance between Si and N atoms for selected species along the N2-to-NH3 conversion. (b) Schematic electrostatic interactions between adsorbates and the bowl active site that break the scaling relations conceptually. (b) schematically depicts the charge distributions of the bowl active site with *N2 and *NH2 that regulate the electrostatic interactions. The initial activation of N2 to *N23? is well stabilized by favorable electrostatics, while the *NH2 and the final *NH3 are driven by repulsion to adsorb weakly on the bridge and top sites of La atoms, respectively. The final *NH3 thus is easily released from the (001)-La surface, recovering the active site for the next catalytic cycle. Conceptually, this breaks the scaling relations between the adsorption energies of *N and *NHx, and this is explicitly confirmed by comparison with other isostructural electride catalysts in the following section.

Fig. 4. The general structure of RTX(001)-R surface (R = Ca, La, Ce; T = Ru, Co, X = Si) with N2 adsorption. (b) The N?N bond lengths and adsorption energies of N2 on the RTX(001)-R surfaces. (c) The correlations of adsorption energies of *N2, *NH and *NH2 with the *N adsorption energy on the RTX(001)-R surfaces and 6 transition metal surfaces. Note that the data for the transition metal surfaces are taken from Ref. [2]. For clarity, the data for the Pd case are not shown here, but are included in Fig. S13.

Fig. 5. Other heterogeneous catalysts that may present the bowl active site design, including the Ru metal surface covered with K cations (a), the (001)-Y terminated surface of YRu2 alloy (b), and the ternay Ru complex hydride with Li cations (c).

References

[1]	F. Abild-Pedersen, J. Greeley, F. Studt, J. Rossmeisl, T. R. Munter, P. G. Moses, E. Skulason, T. Bligaard, J. K. Nørskov, Phys. Rev. Lett., 2007, 99, 016105.
[2]	A. Vojvodic, A. J. Medford, F. Studt, F. Abild-Pedersen, T. S. Khan, T. Bligaard, J. K. Nørskov, Chem. Phys. Lett., 2014, 598, 108-112.
[3]	A. J. Medford, A. Vojvodic, J. S. Hummelshøj, J. Voss, F. Abild-Pedersen, F. Studt, T. Bligaard, A. Nilsson, J. K. Nørskov, J. Catal., 2015, 328, 36-42.
[4]	A. Vojvodic, J. K. Nørskov, Natl. Sci. Rev., 2015, 2, 140-143.
[5]	J. Perez-Ramirez, N. Lopez, Nat. Catal., 2019, 2, 971-976.
[6]	G. Qing, R. Ghazfar, S. T. Jackowski, F. Habibzadeh, M. M. Ashtiani, C. P. Chen, M. R. Smith, T. W. Hamann, Chem. Rev., 2020, 120, 5437-5516.
[7]	H. Liu, L. Wei, F. Liu, Z. Pei, J. Shi, Z. J. Wang, D. He, Y. Chen, ACS Catal., 2019, 9, 5245-5267.
[8]	S. Kim, F. Loose, P. J. Chirik, Chem. Rev., 2020, 120, 5637-5681.
[9]	D. Singh, W. R. Buratto, J. F. Torres, L. J. Murray, Chem. Rev., 2020, 120, 5517-5581.
[10]	K. Tanifuji, Y. Ohki, Chem. Rev., 2020, 120, 5194-5251.
[11]	M. J. Chalkley, M. W. Drover, J. C. Peters, Chem. Rev., 2020, 120, 5582-5636.
[12]	D. V. Yandulov, R. R. Schrock, Science, 2003, 301, 76-78.
[13]	K. Arashiba, Y. Miyake, Y. Nishibayashi, Nat. Chem., 2011, 3, 120-125.
[14]	X. Liu, Y. Jiao, Y. Zheng, M. Jaroniec, S. Z. Qiao, J. Am. Chem. Soc., 2019, 141, 9664-9672.
[15]	X. F. Li, Q. K. Li, J. Cheng, L. Liu, Q. Yan, Y. Wu, X. H. Zhang, Z. Y. Wang, Q. Qiu, Y. Luo, J. Am. Chem. Soc., 2016, 138, 8706-8709.
[16]	C. Choi, S. Back, N. Y. Kim, J. Lim, Y. H. Kim, Y. Jung, ACS Catal., 2018, 8, 7517-7525.
[17]	J. Zhao, Z. Chen, J. Am. Chem. Soc., 2017, 139, 12480-12487.
[18]	X. L. Ma, J. C. Liu, H. Xiao, J. Li, J. Am. Chem. Soc., 2018, 140, 46-49.
[19]	J. C. Liu, X. L. Ma, Y. Li, Y. G. Wang, H. Xiao, J. Li, Nat. Commun., 2018, 9, 1610.
[20]	R. J. Burford, M. D. Fryzuk, Nat. Rev. Chem., 2017, 1, 0026.
[21]	J. Fajardo, J. C. Peters, J. Am. Chem. Soc., 2017, 139, 16105-16108.
[22]	J. B. Lu, X. L. Ma, J. Q. Wang, J. C. Liu, H. Xiao, J. Li, J. Phys. Chem. A, 2018, 122, 4530-4537.
[23]	J. Fajardo, J. C. Peters, Inorg. Chem., 2021, 60, 1220-1227.
[24]	Y. F. Jiang, X. L. Ma, J. B. Lu, J. Q. Wang, H. Xiao, J. Li, Small Methods, 2019, 3, 1800340.
[25]	C. Liu, Q. Li, C. Wu, J. Zhang, Y. Jin, D. R. MacFarlane, C. Sun, J. Am. Chem. Soc., 2019, 141, 2884-2888.
[26]	A. J. Ryan, S. g. Balasubramani, J. W. Ziller, F. Furche, W. J. Evans, J. Am. Chem. Soc., 2020, 142, 9302-9313.
[27]	Y. Tanabe, in: Transition Metal-Dinitrogen Complexes: Preparation, Reactivity, Y. Nishibayashi, eds., Wiley-VCH, Weinheim, 2019, 441-474.
[28]	A. R. Fox, S. C. Bart, K. Meyer, C. C. Cummins, Nature, 2008, 455, 341-349.
[29]	Z. R. Turner, Inorganics, 2015, 3, 597-635.
[30]	X. Xin, I. Douair, Y. Zhao, S. Wang, L. Maron, C. Zhu, J. Am. Chem. Soc., 2020, 142, 15004-15011.
[31]	E. Lu, B. E. Atkinson, A. J. Wooles, J. T. Boronski, L. R. Doyle, F. Tuna, J. D. Cryer, P. J. Cobb, I. J. Vitorica-Yrezabal, G. F. S. Whitehead, N. Kaltsoyannis, S. T. Liddle, Nat. Chem., 2019, 11, 806-811.
[32]	M. Falcone, L. Barluzzi, J. Andrez, F. Fadaei Tirani, I. Zivkovic, A. Fabrizio, C. Corminboeuf, K. Severin, M. Mazzanti, Nat. Chem., 2019, 11, 154-160.
[33]	M. Falcone, L. Chatelain, R. Scopelliti, I. Zivkovic, M. Mazzanti, Nature, 2017, 547, 332-335.
[34]	M. Zhou, X. Jin, Y. Gong, J. Li, Angew. Chem. Int. Ed., 2007, 46, 2911-2914.
[35]	Y. Xiao, X. K. Zhao, T. Wu, J. T. Miller, H. S. Hu, J. Li, W. Huang, P. L. Diaconescu, Chem. Sci., 2021, 12, 227-238.
[36]	P. L. Arnold, T. Ochiai, F. Y. T. Lam, R. P. Kelly, M. L. Seymour, L. Maron, Nat. Chem., 2020, 12, 654-659.
[37]	J. B. Lu, X. L. Ma, J. Q. Wang, Y. F. Jiang, Y. Li, H. S. Hu, H. Xiao, J. Li, Inorg. Chem., 2019, 58, 7433-7439.
[38]	J. Wu, J. Li, Y. Gong, M. Kitano, T. Inoshita, H. Hosono, Angew. Chem. Int. Ed., 2019, 58, 825-829.
[39]	Y. Gong, J. Wu, M. Kitano, J. Wang, T. N. Ye, J. Li, Y. Kobayashi, K. Kishida, H. Abe, Y. Niwa, H. Yang, T. Tada, H. Hosono, Nat. Catal., 2018, 1, 178-185.
[40]	J. Li, J. Wu, H. Wang, Y. Lu, T. Ye, M. Sasase, X. Wu, M. Kitano, T. Inoshita, H. Hosono, Chem. Sci., 2019, 10, 5712-5718.
[41]	S. Dahl, A. Logadottir, C. J. H. Jacobsen, J. K. Nørskov, Appl. Catal. A, 2001, 222, 19-29.
[42]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[43]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[44]	V. Wang, N. Xu, J. C. Liu, G. Tang, W. T. Geng, Comput. Phys. Commun., 2021, 267, 108033.
[45]	M. Raupach, R. Tonner, J. Chem. Phys., 2015, 142, 194105.
[46]	G. T. Velde, F. M. Bickelhaupt, E. J. Baerends, C. Fonseca Guerra, S. J. A. van Gisbergen, J. G. Snijders, T. Ziegler, J. Comput. Chem., 2001, 22, 931-967.
[47]	S. Grimme, S. Ehrlich, L. Goerigk, J. Comput. Chem., 2011, 32, 1456-1465.
[48]	T. Dubé, M. Ganesan, S. Conoci, S. Gambarotta, G. P. A. Yap, Organometallics, 2000, 19, 3716-3721.
[49]	M. R. MacDonald, J. W. Ziller, W. J. Evans, J. Am. Chem. Soc., 2011, 133, 15914-15917.
[50]	M. R. MacDonald, J. E. Bates, J. W. Ziller, F. Furche, W. J. Evans, J. Am. Chem. Soc., 2013, 135, 9857-9868.
[51]	P. B. Hitchcock, M. F. Lappert, L. Maron, A. V. Protchenko, Angew. Chem. Int. Ed., 2008, 47, 1488-1491.
[52]	K. Grubel, W. W. Brennessel, B. Q. Mercado, P. L. Holland, J. Am. Chem. Soc., 2014, 136, 16807-16816.
[53]	S. Suzuki, Y. Ishida, H. Kameo, S. Sakaki, H. Kawaguchi, Angew. Chem. Int. Ed., 2020, 59, 13444-13450.
[54]	A. Logadottir, J. K Nørskov, J. Catal., 2003, 220, 273-279.
[55]	Z. Liu, Acta Phys.-Chim. Sin., 2019, 35, 1171-1172.
[56]	M. E. Fieser, M. R. MacDonald, B. T. Krull, J. E. Bates, J. W. Ziller, F. Furche, W. J. Evans, J. Am. Chem. Soc., 2015, 137, 369-382.
[57]	M. L. Neidig, D. L. Clark, R. L. Martin, Coord. Chem. Rev., 2013, 257, 394-406.
[58]	T. Ogawa, Y. Kobayashi, H. Mizoguchi, M. Kitano, H. Abe, T. Tada, Y. Toda, Y. Niwa, H. Hosono, J. Phys. Chem. C, 2018, 122, 10468-10475.
[59]	Q. Wang, J. Pan, J. Guo, H. A. Hansen, H. Xie, L. Jiang, L. Hua, H. Li, Y. Guan, P. Wang, W. Gao, L. Liu, H. Cao, Z. Xiong, T. Vegge, P. Chen, Nat. Catal., 2021, 4, 959-967.

Breaking the scaling relations for efficient N₂-to-NH₃ conversion by a bowl active site design: Insight from LaRuSi and isostructural electrides

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 5

References

Related Articles 3

Recommended Articles

Metrics

[1]	Lijing Wang, Tianyi Yang, Bo Feng, Xiangyu Xu, Yuying Shen, Zihan Li, Arramel , Jizhou Jiang. Constructing dual electron transfer channels to accelerate CO₂ photoreduction guided by machine learning and first-principles calculation [J]. Chinese Journal of Catalysis, 2023, 54(11): 265-277.
[2]	Ziyi Jiang, Youcheng Hu, Jun Huang, ShengLi Chen. A combinatorial descriptor for volcano relationships of electrochemical nitrogen reduction reaction [J]. Chinese Journal of Catalysis, 2022, 43(11): 2881-2888.
[3]	Chun Zhu, Jin-Xia Liang, Yang Meng, Jian Lin, Zexing Cao. Mn-corrolazine-based 2D-nanocatalytic material with single Mn atoms for catalytic oxidation of alkane to alcohol [J]. Chinese Journal of Catalysis, 2021, 42(6): 1030-1039.