Strong metal-support interaction boosts the electrocatalytic hydrogen evolution capability of Ru nanoparticles supported on titanium nitride

Abstract

Ruthenium (Ru) has been regarded as one of the most promising alternatives to substitute Pt for catalyzing alkaline hydrogen evolution reaction (HER), owing to its inherent high activity and being the cheapest platinum-group metal. Herein, based on the idea of strong metal-support interaction (SMSI) regulation, Ru/TiN catalysts with different degrees of TiN overlayer over Ru nanoparticles were fabricated, which were applied to the alkaline electrolytic water. Characterizations reveal that the TiN overlayer would gradually encapsulate the Ru nanoparticles and induce more electron transfer from Ru nanoparticles to TiN support by the Ru-N-Ti bond as the SMSI degree increased. Further study shows that the exposed Ru-TiN interfaces greatly promote the H₂ desorption capacity. Thus, the Ru/TiN-300 with a moderate SMSI degree exhibits excellent HER performance, with an overpotential of 38 mV at 10 mA cm^-2. Also, due to the encapsulation role of TiN overlayer on Ru nanoparticles, it displays super long-term stability with a very slight potential change after 24 h. This study provides a deep insight into the influence of the SMSI effect between Ru and TiN on HER and offers a novel approach for preparing efficient and stable HER electrocatalysts through SMSI engineering.

Keywords

electronic structure / hydrogen evolution reaction / ruthenium / strong metal-support interaction / titanium nitride

References

[1] Hu Q, Wang Z, Huang X, et al. A unique space confined strategy to construct defective metal oxides within porous nanofibers for electrocatalysis. Energy Environ Sci. 2020; 13 (12): 5097- 5103.

[2] Deng C, Toe CY, Li X, et al. Earth-abundant metal-based electrocatalysts promoted anodic reaction in hybrid water electrolysis for efficient hydrogen production: recent progress and perspectives. Adv Energy Mater. 2022; 12 (25): 2201047.

[3] Yang X, Ben H, Ragauskas AJ. Recent advances in the synthesis of deuterium-labeled compounds. Asian J Org Chem. 2021; 10 (10): 2473- 2485.

[4] Hu Q, Gao K, Wang X, et al. Subnanometric Ru clusters with upshifted D band center improve performance for alkaline hydrogen evolution reaction. Nat Commun. 2022; 13: 3958.

[5] Wang K, Wang S, Hui KS, et al. Synergistically boosting the elementary reactions over multiheterogeneous ordered macroporous Mo₂C/NC-Ru for highly efficient alkaline hydrogen evolution. Carbon Energy. 2022; 4 (5): 856- 866.

[6] Zhang YY, Zhang N, Peng P, et al. Uniformly dispersed Ru nanoparticles constructed by in situ confined polymerization of ionic liquids for the electrocatalytic hydrogen evolution reaction. Small Methods. 2021; 5 (7): 2100505.

[7] Su P, Pei W, Wang X, et al. Exceptional electrochemical HER performance with enhanced electron transfer between Ru nanoparticles and single atoms dispersed on a carbon substrate. Angew Chem. 2021; 133 (29): 16180- 16186.

[8] Tang J, Wang B, Zhang Y, et al. One-step integration of amorphous RuBx and crystalline Ru nanoparticles into B/N-doped porous carbon polyhedra for robust electrocatalytic activity towards the HER in both acidic and basic media. J Mater Chem A. 2022; 10 (8): 4181- 4190.

[9] De Rogatis L, Cargnello M, Gombac V, Lorenzut B, Montini T, Fornasiero P. Embedded phases: a way to active and stable catalysts. ChemSusChem. 2010; 3 (1): 24- 42.

[10] Alinezhad A, Gloag L, Benedetti TM, et al. Direct growth of highly strained Pt islands on branched Ni nanoparticles for improved hydrogen evolution reaction activity. J Am Chem Soc. 2019; 141 (41): 16202- 16207.

[11] van Deelen TW, Hernández Mejía C, de Jong KP. Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity. Nat Catal. 2019; 2 (11): 955- 970.

[12] Jiang ZZ, Wang ZB, Chu YY, Gu DM, Yin GP. Carbon riveted microcapsule Pt/MWCNTs-TiO₂ catalyst prepared by in situ carbonized glucose with ultrahigh stability for proton exchange membrane fuel cell. Energy Environ Sci. 2011; 4 (7): 2558- 2566.

[13] Vayssilov GN, Lykhach Y, Migani A, et al. Support nanostructure boosts oxygen transfer to catalytically active platinum nanoparticles. Nat Mater. 2011; 10 (4): 310- 315.

[14] Mao X, Foucher AC, Montini T, Stach EA, Fornasiero P, Gorte RJ. Epitaxial and strong support interactions between Pt and LaFeO₃ films stabilize Pt dispersion. J Am Chem Soc. 2020; 142 (23): 10373- 10382.

[15] Tauster SJ, Fung SC, Garten RL. Strong metal-support interactions. Group 8 noble metals supported on titanium dioxide. J Am Chem Soc. 1978; 100 (1): 170- 175.

[16] Liu JJ. Advanced electron microscopy of metal-support interactions in supported metal catalysts. ChemCatChem. 2011; 3 (6): 934- 948.

[17] Gao Y, Liang Y, Chambers SA. Thermal stability and the role of oxygen vacancy defects in strong metal support interaction—Pt on Nb-doped TiO₂(100). Surf Sci. 1996; 365 (3): 638- 648.

[18] Li Y, Zhang Y, Qian K, Huang W. Metal-support interactions in metal/oxide catalysts and oxide-metal interactions in oxide/metal inverse catalysts. ACS Catal. 2022; 12 (2): 1268- 1287.

[19] Tang H, Su Y, Zhang B, et al. Classical strong metal-support interactions between gold nanoparticles and titanium dioxide. Sci Adv. 2017; 3 (10): e1700231.

[20] Zhang Y, Yang X, Yang X, et al. Tuning reactivity of Fischer-Tropsch synthesis by regulating TiO_x overlayer over Ru/TiO₂ nanocatalysts. Nat Commun. 2020; 11: 3185.

[21] Zhang Y, Yan W, Qi H, et al. Strong metal-support interaction of Ru on TiO₂ derived from the Co-reduction mechanism of Ru_xTi_1-xO₂ interphase. ACS Catal. 2022; 12 (3): 1697- 1705.

[22] Dong J, Fu Q, Jiang Z, Mei B, Bao X. Carbide-supported Au catalysts for water-gas shift reactions: a new territory for the strong metal-support interaction effect. J Am Chem Soc. 2018; 140 (42): 13808- 13816.

[23] Zhang J, Ma J, Choksi TS, et al. Strong metal-support interaction boosts activity, selectivity, and stability in electrosynthesis of H₂O₂. J Am Chem Soc. 2022; 144 (5): 2255- 2263.

[24] Chen Z, Zeng X, Li X, Lv Z, Li J, Zhang Y. Strong metal phosphide-phosphate support interaction for enhanced nonnoble metal catalysis. Adv Mater. 2022; 34 (5): 2106724.

[25] Yang Y, Wu D, Li R, et al. Engineering the strong metal support interaction of titanium nitride and ruthenium nanorods for effective hydrogen evolution reaction. Appl Catal B. 2022; 317: 121796.

[26] Yan QQ, Wu DX, Chu SQ, et al. Reversing the charge transfer between platinum and sulfur-doped carbon support for electrocatalytic hydrogen evolution. Nat Commun. 2019; 10: 4977.

[27] Zhou H, Liu T, Zhao X, et al. A supported nickel catalyst stabilized by a surface digging effect for efficient methane oxidation. Angew Chem Int Ed. 2019; 58 (51): 18388- 18393.

[28] Yao B, Li M, Zhang J, et al. TiN paper for ultrafast-charging supercapacitors. Nano-Micro Lett. 2020; 12 (1): 3.

[29] Zhang F, Liu T, Li M, et al. Multiscale pore network boosts capacitance of carbon electrodes for ultrafast charging. Nano Lett. 2017; 17 (5): 3097- 3104.

[30] Chen P, Khetan A, Yang F, et al. Experimental and theoretical understanding of nitrogen-doping induced strong metal-support interactions in Pd/TiO₂ catalysts for nitrobenzene hydrogenation. ACS Catal. 2017; 7 (2): 1197- 1206.

[31] Chen X, Gierlich CH, Schötz S, et al. Hydrogen production based on liquid organic hydrogen carriers through sulfur doped platinum catalysts supported on TiO₂. ACS Sustainable Chem Eng. 2021; 9 (19): 6561- 6573.

[32] Lentz C, Jand SP, Melke J, Roth C, Kaghazchi P. DRIFTS study of CO adsorption on Pt nanoparticles supported by DFT calculations. J Mol Catal A: Chem. 2017; 426: 1- 9.

[33] Cheah SK, Bernardet VP, Franco AA, Lemaire O, Gelin P. Study of CO and hydrogen interactions on carbon-supported Pt nanoparticles by quadrupole mass spectrometry and Operando diffuse reflectance FTIR spectroscopy. J Phys Chem C. 2013; 117 (44): 22756- 22767.

[34] Liu H, Hu Z, Liu Q, et al. Single-atom Ru anchored in nitrogen-doped MXene (Ti₃C₂T_x) as an efficient catalyst for the hydrogen evolution reaction at all pH values. J Mater Chem A. 2020; 8 (46): 24710- 24717.

[35] Zhang P, Wu T, Jiang T, et al. Ru-Zn supported on hydroxyapatite as an effective catalyst for partial hydrogenation of benzene. Green Chem. 2013; 15 (1): 152- 159.

[36] Shao ZL, Liu XF, Zhang SN, Wang H, Sun YH. CO hydrogenation to ethanol over supported Rh-based catalyst: effect of the support. Acta Phys Chim Sin. 2021; 37 (10): 1911053.

[37] Peng Z, Jia D, Al-Enizi AM, Elzatahry AA, Zheng G. From water oxidation to reduction: homologous Ni-Co based nanowires as complementary water splitting electrocatalysts. Adv Energy Mater. 2015; 5 (9): 1402031.

[38] Luo W, Wang Y, Cheng C. Ru-based electrocatalysts for hydrogen evolution reaction: recent research advances and perspectives. Mater Today Phys. 2020; 15: 100274.

[39] Wang T, Wang X, Liu Y, Zheng J, Li X. A highly efficient and stable biphasic nanocrystalline Ni-Mo-N catalyst for hydrogen evolution in both acidic and alkaline electrolytes. Nano Energy. 2016; 22: 111- 119.

[40] Liu Z, Zeng L, Yu J, et al. Charge redistribution of Ru nanoclusters on Co₃O₄ porous nanowire via the oxygen regulation for enhanced hydrogen evolution reaction. Nano Energy. 2021; 85: 105940.

[41] Kong X, Xu K, Zhang C, et al. Free-standing two-dimensional Ru nanosheets with high activity toward water splitting. ACS Catal. 2016; 6 (3): 1487- 1492.

[42] Jiang P, Yang Y, Shi R, et al. Pt-like electrocatalytic behavior of Ru-MoO₂ nanocomposites for the hydrogen evolution reaction. J Mater Chem A. 2017; 5 (11): 5475- 5485.

[43] Falconer JL, Schwarz JA. Temperature-programmed desorption and reaction: applications to supported catalysts. Catal Rev. 1983; 25 (2): 141- 227.

[44] Paál Z, Menon PG. Hydrogen effects in metal catalysts. Catal Rev. 1983; 25 (2): 229- 324.

[45] Lin HY, Chen YW. The kinetics of H₂ adsorption on supported ruthenium catalysts. Thermochim Acta. 2004; 419 (1-2): 283- 290.

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