Fine RuCuP Nanoclusters Anchored on TiO₂ for Efficient Hydrolysis of Ammonia Borane

Abstract

We synthesized Ru₁Cu₂₅P_7.5/TiO₂ catalyst using sodium borohydride (NaBH₄) as reductant in a facile strategy. The highly dispersed RuCuP nanoclusters are anchored on the TiO₂ surface with an average particle size of 2.62 nm. The catalyst shows excellent catalytic activity when applied to the hydrolysis of AB, which owns a high turnover frequency value of 531.56 mol_H2mol_Ru⁻¹min⁻¹ and a low activation energy of 46.38 kJ · mol⁻¹, it also exhibits good durability which maintains 61.13% initial activity after five cycles. The high catalytic performance of Ru₁Cu₂₅P_7.5/TiO₂ may be attributed to the synergistic effects between Ru, Cu, and P elements, fine particle size, good dispersion, and the tight adhesion between nanoclusters and carrier.

Keywords

ammonia borane / hydrogen / nanoclusters / transition metal phosphides

References

[1] Gu BN, Sun T, Wang Y, et al. . Maximizing Hydrogen Production by AB Hydrolysis with Pt@ Cobalt Oxide/N, O-Rich Carbon and Alkaline Ultrasonic Irradiation. Inorganic Chemistry Frontiers, 2022, 9(10): 2 204-2 212 J]

[2] Baghban A, Habibzadeh S, Zokaee Ashtiani F. Activity of Transition Metals in N-Doped Carbon Electrocatalysts for Hydrogen Evolution Reaction: Insight from Quantum Chemistry Computations. International Journal of Energy Research, 2022, 46(2): 1 637-1 645 J]

[3] Hou CC, Li Q, Wang CJ, et al. . Ternary Ni-Co-P Nanoparticles as Noble-Metal-Free Catalysts to Boost the Hydrolytic Dehydrogenation of Ammonia-Borane. Energy & Environmental Science, 2017, 10(8): 1 770-1 776 J]

[4] Song HQ, Cheng YJ, Li BJ, et al. . Carbon Dots and RuP₂ Nanohybrid as an Efficient Bifunctional Catalyst for Electrochemical Hydrogen Evolution Reaction and Hydrolysis of Ammonia Borane. ACS Sustainable Chemistry & Engineering, 2020, 8(9): 3 995-4 002 J]

[5] Yuan M, Zhong ST, Li G, et al. . Architecture of Urchin-like TiO₂ Integrated Ultrasmall Rh Nanoparticles with Oxygen Vacancy-Reinforced Electronic Metal-Support Interaction for Boosting Hydrogen Production from Ammonia Borane Hydrolysis. Fuel, 2024, 358: 130 200 J]

[6] Wei QH, Qiu SJ, Yin CW, et al. . Nitrogen-Doped Carbon Encapsulated Ru-Decorated Co₂P Supported on Graphene Oxide as Efficient Catalysts for Hydrogen Generation from Ammonia Borane. Journal of Alloys and Compounds, 2022, 921: 166 207 J]

[7] Lu D, Yu GF, Li Y, et al. . RuCo NPs Supported on MIL-96 (Al) as Highly Active Catalysts for the Hydrolysis of Ammonia Borane. Journal of Alloys and Compounds, 2017, 694: 662-671 J]

[8] Chen YF, Feng K, Yuan GT, et al. . Highly Efficient CoNiP Nanoboxes on Graphene Oxide for the Hydrolysis of Ammonia Borane. Chemical Engineering Journal, 2022, 428: 131 219 J]

[9] Deng J, Zhou XL, Zou JD, et al. . PdCo Alloy Supported on a ZIF-Derived N-Doped Carbon Hollow Polyhedron for Dehydrogenation of Ammonia Borane. ACS Applied Energy Materials, 2022, 5(6): 7 408-7 419 J]

[10] Kalkan EB, Akbayrak S, Özkar S. Ruthenium (0) Nanoparticles Supported on Nanohafnia: A Highly Active and Long-Lived Catalyst in Hydrolytic Dehydrogenation of Ammonia Borane. Molecular Catalysis, 2017, 430: 29-35 J]

[11] Xu WJ, Li W, Wen H, et al. . Metal/Metal-Organic Framework Interfacial Ensemble-Induced Dual Site Catalysis towards Hydrogen Generation. Applied Catalysis B: Environmental, 2021, 286: 119 946 J]

[12] Wu H, Cheng YJ, Fan YP, et al. . Metal-Catalyzed Hydrolysis of Ammonia Borane: Mechanism, Catalysts, and Challenges. International Journal of Hydrogen Energy, 2020, 45(55): 30 325-30 340 J]

[13] Chandra M, Xu Q. A High-Performance Hydrogen Generation System: Transition Metal-Catalyzed Dissociation and Hydrolysis of Ammonia-Borane. Journal of Power Sources, 2006, 156(2): 190-194 J]

[14] Zhang H, Gu XJ, Liu PL, et al. . Highly Efficient Visible-Light-Driven Catalytic Hydrogen Evolution from Ammonia Borane Using Non-Precious Metal Nanoparticles Supported by Graphitic Carbon Nitride. Journal of Materials Chemistry A, 2017, 5(5): 2 288-2 296 J]

[15] Asim M, Zhang SG, Wang YT, et al. . Self-Supporting NiCoP for Hydrogen Generation via Hydrolysis of Ammonia Borane. Fuel, 2022, 318: 123 544 J]

[16] Li HJ, Yan YF, Feng S, et al. . Highly Efficient Photothermal Difunctional Catalysts to Enhance Ammonia Borane Hydrolysis for Hydrogen Evolution. Energy & Fuels, 2020, 34(12): 16 948-16 955 J]

[17] Xiong X, Zhou LQ, Yu GF, et al. . Synthesis and Catalytic Performance of a Novel RuCuNi/CNTs Nanocomposite in Hydrolytic Dehydrogenation of Ammonia Borane. International Journal of Hydrogen Energy, 2015, 40(45): 15 521-15 528 J]

[18] Li YT, Zhang XL, Peng ZK, et al. . Hierarchical Porous g-C₃N₄ Coupled Ultrafine RuNi Alloys as Extremely Active Catalysts for the Hydrolytic Dehydrogenation of Ammonia Borane. ACS Sustainable Chemistry & Engineering, 2020, 8(22): 8 458-8 468 J]

[19] Wu H, Cheng YJ, Wang BY, et al. . Carbon Dots-Confined CoP-CoO Nanoheterostructure with Strong Interfacial Synergy Triggered the Robust Hydrogen Evolution from Ammonia Borane. Journal of Energy Chemistry, 2021, 57: 198-205 J]

[20] Fu ZC, Xu Y, Chan SLF, et al. . Highly Efficient Hydrolysis of Ammonia Borane by Anion (⁻OH, F⁻, Cl⁻)-Tuned Interactions between Reactant Molecules and CoP Nanoparticles. Chemical Communications, 2017, 53(4): 705-708 J]

[21] Du YS, Liu C, Cheng GZ, et al. . Cuboid Ni₂P as a Bifunctional Catalyst for Efficient Hydrogen Generation from Hydrolysis of Ammonia Borane and Electrocatalytic Hydrogen Evolution. Chemistry-An Asian Journal, 2017, 12(22): 2 967-2 972 J]

[22] Qu B, Tao Y, Yang L, et al. . One-Pot Co-Reduction Synthesis of Orange-like Pd@Co@P Nanoparticles Supported on rGO for Catalytic Hydrolysis of Ammonia Borane. International Journal of Hydrogen Energy, 2021, 46(61): 31 324-31 333 J]

[23] Zhou X, Meng XF, Wang JM, et al. . Boron Nitride Supported NiCoP Nanoparticles as Noble Metal-Free Catalyst for Highly Efficient Hydrogen Generation from Ammonia Borane. International Journal of Hydrogen Energy, 2019, 44(10): 4 764-4 770 J]

[24] Wang C, Wang ZL, Wang HL, et al. . Noble-Metal-Free Co@ Co₂P/N-Doped Carbon Nanotube Polyhedron as an Efficient Catalyst for Hydrogen Generation from Ammonia Borane. International Journal of Hydrogen Energy, 2021, 46(13): 9 030-9 039 J]

[25] Yan LT, Jiang HM, Xing YL, et al. . Nickel Metal-Organic Framework Implanted on Graphene and Incubated to be Ultrasmall Nickel Phosphide Nanocrystals Acts as a Highly Efficient Water Splitting Electrocatalyst. Journal of Materials Chemistry A, 2018, 6(4): 1 682-1 691 J]

[26] Liu P, Rodriguez JA. Catalysts for Hydrogen Evolution from the [NiFe] Hydrogenase to the Ni₂P (001) Surface: The Importance of Ensemble Effect. Journal of the American Chemical Society, 2005, 127(42): 14 871-14 878 J]

[27] Kibsgaard J, Tsai C, Chan KR, et al. . Designing an Improved Transition Metal Phosphide Catalyst for Hydrogen Evolution Using Experimental and Theoretical Trends. Energy & Environmental Science, 2015, 8(10): 3 022-3 029 J]

[28] Yang BB, Xu JY, Bin D, et al. . Amorphous Phosphatized Ruthenium-Iron Bimetallic Nanoclusters with Pt-like Activity for Hydrogen Evolution Reaction. Applied Catalysis B: Environmental, 2021, 283: 119 583 J]

[29] Du C, Yang L, Yang FL, et al. . Nest-like NiCoP for Highly Efficient Overall Water Splitting. ACS Catalysis, 2017, 7(6): 4 131-4 137 J]

[30] Yang J, Cui ZK, Ma JT, et al. . Ru Coated Co Nanoparticles Decorated on Cotton Derived Carbon Fibers as a Highly Efficient and Magnetically Recyclable Catalyst for Hydrogen Generation from Ammonia Borane. International Journal of Hydrogen Energy, 2018, 43(3): 1 355-1 364 J]

[31] Su LX, Jin YM, Gong D, et al. . The Role of Discrepant Reactive Intermediates on Ru-Ru₂P Heterostructure for pH-Universal Hydrogen Oxidation Reaction. Angewandte Chemie International Edition, 2023, 62(2): e202 215 585 J]

[32] Sun YM, Xue ZQ, Liu QL, et al. . Modulating Electronic Structure of Metal-Organic Frameworks by Introducing Atomically Dispersed Ru for Efficient Hydrogen Evolution. Nature Communications, 2021, 12(1): 1 369 J]

[33] Lv H, Wei R, Guo XW, et al. . Synergistic Catalysis of Binary RuP Nanoclusters on Nitrogen-Functionalized Hollow Mesoporous Carbon in Hydrogen Production from the Hydrolysis of Ammonia Borane. The Journal of Physical Chemistry Letters, 2021, 12(1): 696-703 J]

[34] Xu CW, Wang Z, Chen C, et al. . Constructing MOF-199 Anchored RuMoP Nanoparticles as a High-Performance Catalyst for Boosting the Hydrolysis of AB. International Journal of Hydrogen Energy, 2023, 48(39): 14 670-14 680 J]

[35] Shen YZ, Liu FS, Li WC, et al. D-Band Center Modulation of Supported Ru on Phosphorous Doped Black TiO₂ for Efficient Hydrogen Generation[J]. Chemical Engineering Journal, 2024: 153 251

[36] Zaier I, Eroglu Z, Metin Ö. A Facile Preparation of Graphene Hydrogel-Supported Bimetallic RuM (M: Co, Ni, Cu) Nanoparticles as Catalysts in the Hydrogen Generation from Ammonia Borane. Pure and Applied Chemistry, 2023, 95(6): 655-669 J]

[37] Gao YX, Zhang HW, Han AJ, et al. . Ru/ZrO₂ Catalysts for Transfer Hydrogenation of Levulinic Acid with Formic Acid/Formate Mixtures: Importance of Support Stability. ChemistrySelect, 2018, 3(5): 1 343-1 351 J]

[38] Huang XY, Liu YY, Wen H, et al. . Ensemble-Boosting Effect of Ru-Cu Alloy on Catalytic Activity towards Hydrogen Evolution in Ammonia Borane Hydrolysis. Applied Catalysis B: Environmental, 2021, 287: 119 960 J]

[39] Song Q, Wang WD, Hu XW, et al. . Ru Nanoclusters Confined in Porous Organic Cages for Catalytic Hydrolysis of Ammonia Borane and Tandem Hydrogenation Reaction. Nanoscale, 2019, 11(44): 21 513-21 521 J]

[40] Ruppert AM, Jędrzejczyk M, Sneka-Platek O, et al. . Ru Catalysts for Levulinic Acid Hydrogenation with Formic Acid as a Hydrogen Source. Green Chemistry, 2016, 18(7): 2 014-2 028 J]

[41] Zhang JP, Li J, Yang LJ, et al. . Efficient Hydrogen Production from Ammonia Borane Hydrolysis Catalyzed by TiO₂-Supported RuCo Catalysts. International Journal of Hydrogen Energy, 2021, 46(5): 3 964-3 973 J]

[42] Jin YC, Chen FY, Wang JL, et al. . Tuning Electronic and Composition Effects in Ruthenium-Copper Alloy Nanoparticles Anchored on Carbon Nanofibers for Rechargeable Li-CO2 Batteries. Chemical Engineering Journal, 2019, 375: 121 978 J]

[43] Ma XX, Chang YQ, Zhang Z, et al. . Forest-like NiCoP@ Cu₃P Supported on Copper Foam as a Bifunctional Catalyst for Efficient Water Splitting. Journal of Materials Chemistry A, 2018, 6(5): 2 100-2 106 J]

[44] Cao N, Hu K, Luo W, et al. . RuCu Nanoparticles Supported on Graphene: A Highly Efficient Catalyst for Hydrolysis of Ammonia Borane. Journal of Alloys and Compounds, 2014, 590: 241-246 J]

[45] Cao N, Su J, Luo W, et al. . Graphene Supported Ru@Co Core-Shell Nanoparticles as Efficient Catalysts for Hydrogen Generation from Hydrolysis of Ammonia Borane and Methylamine Borane. Catalysis Communications, 2014, 43: 47-51 J]

[46] Yang KZ, Zhou LQ, Xiong X, et al. . RuCuCo Nanoparticles Supported on MIL-101 as a Novel Highly Efficient Catalysts for the Hydrolysis of Ammonia Borane. Microporous and Mesoporous Materials, 2016, 225: 1-8 J]

[47] Akbayrak S, Tonbul Y, Özkar S. Ceria-Supported Ruthenium Nanoparticles as Highly Active and Long-Lived Catalysts in Hydrogen Generation from the Hydrolysis of Ammonia Borane. Dalton Transactions, 2016, 45(27): 10 969-10 978 J]

[48] Akbayrak S, Tanyildizi S, Morkan İ, et al. . Ruthenium (0) Nanoparticles Supported on Nanotitania as Highly Active and Reusable Catalyst in Hydrogen Generation from the Hydrolysis of Ammonia Borane. International Journal of Hydrogen Energy, 2014, 39(18): 9 628-9 637 J]

[49] Rakap M. Hydrogen Generation from Hydrolysis of Ammonia Borane in the Presence of Highly Efficient Poly (N-vinyl-2-Pyrrolidone)-Protected Platinum-Ruthenium Nanoparticles. Applied Catalysis A: General, 2014, 478: 15-20 J]

[50] Fan YR, Li XJ, He XC, et al. . Effective Hydrolysis of Ammonia Borane Catalyzed by Ruthenium Nanoparticles Immobilized on Graphic Carbon Nitride. International Journal of Hydrogen Energy, 2014, 39(35): 19 982-19 989 J]

[51] Fang Y, Li JL, Togo T, et al. . Ultra-Small Face-Centered-Cubic Ru Nanoparticles Confined within a Porous Coordination Cage for Dehydrogenation. Chem, 2018, 4(3): 555-563 J]

[52] Rablen PR. Large Effect on Borane Bond Dissociation Energies Resulting from Coordination by Lewis Bases. Journal of the American Chemical Society, 1997, 119(35): 8 350-8 360 J]

[53] Wang CL, Tuninetti J, Wang Z, et al. . Hydrolysis of Ammonia-Borane over Ni/ZIF-8 Nanocatalyst: High Efficiency, Mechanism, and Controlled Hydrogen Release. Journal of the American Chemical Society, 2017, 139(33): 11 610-11 615 J]

[54] Peebles LR, Marshall P. High-Accuracy Coupled-Cluster Computations of Bond Dissociation Energies in SH, H₂S, and H₂O. The Journal of Chemical Physics, 2002, 117(7): 3 132-3 138 J]

[55] Yang SY, He P, Tian Y, et al. . In Situ Encapsulating Cobalt Phosphide into a Quasi-MOF: A High-Performance Catalyst for Hydrolytic Dehydrogenation of Ammonia Borane. New Journal of Chemistry, 2023, 47(6): 3 151-3 158 J]

[56] Ghosh S, Kadam SR, Houben L, et al. . Nickel Phosphide Catalysts for Hydrogen Generation through Water Reduction, Ammonia-Borane and Borohydride Hydrolysis. Applied Materials Today, 2020, 20: 100 693 J]

[57] Wan XQ, Qian DD, Ai LH, et al. . Highly Efficient Peroxymonosulfate Activation by Surface Oxidized Nickel Phosphide with Dual Active Sites. Industrial & Engineering Chemistry Research, 2020, 59(51): 22 040-22 048 J]

[58] Wei ZH, Liu Y, Peng ZK, et al. . Cobalt-Ruthenium Nanoalloys Parceled in Porous Nitrogen-Doped Graphene as Highly Efficient Difunctional Catalysts for Hydrogen Evolution Reaction and Hydrolysis of Ammonia Borane. ACS Sustainable Chemistry & Engineering, 2019, 7(7): 7 014-7 023 J]

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