玉米秸秆担载CoNi合金催化氨硼烷制氢性能的研究

doi:10.15541/jim20260073

摘要/Abstract

摘要： 氨硼烷(NH₃BH₃,AB)是一种固态储氢材料,开发高效、低成本且稳定催化AB分解制氢的催化剂是其工业化应用的关键。本研究采用初加工粉末玉米秸秆(corn straw)作为载体,通过NaBH₄还原制备玉米秸秆担载CoNi合金催化剂(Co_0.75Ni_0.25/CS-y)。室温条件下Co_0.75Ni_0.25/CS-y具有高效催化AB水解制氢活性,最优样品Co_0.75Ni_0.25/CS-20催化性能优于纯Co、纯Ni和Co_0.75Ni_0.25合金。玉米秸秆对Co_0.75Ni_0.25合金具有很好的分散和固定作用,并且Co和Ni原子之间相互作用促进了催化活性的提升。Co_0.75Ni_0.25/CS-20催化AB制氢的平均转换频率(TOF)为7.77 molH2∙molcat.-1∙min-1,其活化能(E_a)为20.17 kJ/mol。此外,Co_0.75Ni_0.25/CS-20催化AB水解制氢具有优异的稳定性,第6次循环催化剂的产率和活性分别为初次反应的100%和82.3%,性能优于多数已报道非贵金属催化剂,甚至优于部分已报道贵金属催化剂。该研究还为非贵金属催化剂的设计提供了新思路,也为生物质材料的高值化利用指明了新方向。

关键词: 氢能, 氨硼烷, CoNi合金, 生物质

Abstract: Ammonia borane (NH₃BH₃, AB) serves as a solid hydrogen storage material, and the preparation of efficient, low-cost, and stable catalysts for the decomposition of AB is crucial for its industrial application. This study prepared a pre-processed powdered corn straw-supported CoNi alloy catalyst (Co_0.75Ni_0.25/CS-y) via reduction by NaBH₄. Co_0.75Ni_0.25/CS-y exhibited high efficiency in the catalytic decomposition of AB for hydrogen evolution under room temperature. Notably, the optimal sample Co_0.75Ni_0.25/CS-20 exhibits superior catalytic activity compared to pure Co, pure Ni and Co_0.75Ni_0.25 alloy. The corn straw effectively dispersed and immobilized the Co_0.75Ni_0.25 alloy, while the cooperation of Co and Ni atoms further enhanced the catalytic activity. Co_0.75Ni_0.25/CS-20 achieved an average turnover frequency (TOF) of 7.77 molH2∙molcat.-1∙min-1 and an activation energy (E_a) of 20.17 kJ/mol. Furthermore, Co_0.75Ni_0.25/CS-20 exhibits excellent yield and activity stability for AB catalytic hydrogen evolution which are 100% and 82.3% of the initial reaction within 6th cycle, respectively. Its performance surpasses most reported non-precious metal catalysts and even outperforms some reported precious metal catalysts. This study introduces novel concepts for the design of non-precious metal catalysts and suggests new avenues for the high-value utilization of biomass materials.

Key words: hydrogen, ammonia borane, CoNi alloy, biomass

中图分类号:

TK91

宋立之, 伍明, 刘鹏飞, 韩冬, 宋二红. 玉米秸秆担载CoNi合金催化氨硼烷制氢性能的研究[J]. 无机材料学报, DOI: 10.15541/jim20260073.

SONG Lizhi, WU Ming, LIU Pengfei, HAN Dong, SONG Erhong. Corn Straw Supported CoNi Alloy for Catalytic Hydrogen Evolution from Ammonia Borane[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260073.

参考文献

[1] ZHANG X Y, ZHU L F, CAO J L,et al. Solar trap-adsorption photocathode for highly stable 2.4 V dual-ion solid-state iodine batteries. Advanced Materials, 2025, 37(42): e04492.
[2] JIANG Z Y, YANG X, ZHANG J,et al. From conventional two‐electron to emerging multi‐electron zinc‐iodine batteries: advantages, challenges, and future perspectives. Advanced Functional Materials, 2025, 35(50): e11754.
[3] CHEN L B, SHENG Y, WU M,et al. Na and O co-doped carbon nitride for efficient photocatalytic hydrogen evolution. Journal of Inorganic Materials, 2025, 40(5): 552.
[4] LI J P, DONG W K, ZHU Z B,et al. Optimizing interfacial charge dynamics and quantum effects in heterodimensional superlattices for efficient hydrogen production. Advanced Science, 2025, 12(6): 2412805.
[5] XIAO M X, LI MM, SONG EH, et al. Halogenated Ti₃C₂ MXene as high capacity electrode material for Li-ion batteries. Journal of Inorganic Materials, 2022, 37(6): 660.
[6] GU Y, WANG H L, ZHANG Y H, et al. Exploiting tripeptide in Pd/C for boosting hydrogen production from formic acid dehydrogenation. Catalysis Science & Technology, 2025, 15(1): 107.
[7] WANG H L, WANG Z L, LIU X,et al. AuPd nanocatalysts supported on citric acid-modified boron nitride to boost hydrogen generation from formic acid dehydrogenation. ACS Applied Nano Materials, 2023, 6(5): 3285.
[8] GAO R, MENG Z, SHI M M,et al. Rapid and complete hydrazine borane decomposition for hydrogen production catalyzed by CoPt/CNTs at room temperature. International Journal of Hydrogen Energy, 2024, 88: 538.
[9] WANG H L, CHI Y, GAO D W, et al. Enhancing formic acid dehydrogenation for hydrogen production with the metal/organic interface. Applied Catalysis B: Environmental, 2019, 255: 117776.
[10] LI X G, YAO L H, YAO Q L, et al. Dehydrogenation of sodium borohydride and ammonia borane over cobalt-based catalysts: advances and prospects. Inorganic Chemistry Frontiers, 2025, 12(18): 5222.
[11] LI M T, LIU J H, ZHANG W K,et al. Fabrication of nano Pt-Co-Cu sites in the heterostructured catalysts for hydrogen generation. ACS Applied Nano Materials, 2024, 7(18): 22061.
[12] CONG W W, ZHANG H X, BING L C,et al. CoNi Nanoparticles supported on hierarchical SAPO-34 zeolite as a catalyst for the hydrolytic dehydrogenation of ammonia borane. ACS Applied Nano Materials, 2023, 6(23): 21991.
[13] ZHANG Z H, LIU L C, ZHANG C X,et al. The doped Co on Rh/Ni@Ni-N-C that weakened the catalytic performance for ammonia borane hydrolysis. International Journal of Hydrogen Energy, 2023, 48(7): 2640.
[14] XU R C, LI H M, XU L X,et al. Interfacial synergy between Pt₃Co nanoparticles and CoO for efficient ammonia borane hydrolysis. Chemical Engineering Journal, 2024, 479: 147773.
[15] XIN Z Y, GUO R H, WUREN T Y,et al. Pt-Fe/GO nanocatalysts: preparation and electrocatalytic performance on ethanol oxidation. Journal of Inorganic Materials, 2025, 40(4): 379.
[16] JIANG R F, YANG M, MENG J K,et al. Enhanced catalytic performance of CuNi bimetallic nanoparticles for hydrogen evolution from ammonia borane hydrolysis. International Journal of Hydrogen Energy, 2023, 48(48): 18245.
[17] CHOU C C, CHEN B H, Hydrogen generation from deliquescence of ammonia borane using Ni-Co/r-GO catalyst.Journal of Power Sources, 2015, 293: 343.
[18] YAN J M, WANG Z L, WANG H L,et al. Rapid and energy-efficient synthesis of a graphene-CuCo hybrid as a high performance catalyst. Journal of Materials Chemistry, 2012, 22: 10990.
[19] CHEN Y X, MU J, ZHANG Y,et al. The effect of heat treatment on the catalytic properties of Fe₅Ni₁₅Cr₁₀Co₁₀Mn₆₀ alloy for NH₃BH₃ hydrolysis. Journal of Materials Science, 2025, 60(31): 13326.
[20] LI Q, CHEN Y M, LIU Y,et al. Synergistic enhancement of Co doped Ni/NiOx nanofilms for catalytic hydrolysis towards ammonia borane. International Journal of Hydrogen Energy, 2024, 95: 604.
[21] PORNEA A M, MEDHEN W A, KIM H,et al. Ternary NiCoP urchin like 3D nanostructure supported on nickel foam as a catalyst for hydrogen generation of alkaline NaBH₄. Chemical Physics, 2019, 516: 152.
[22] WANG C, WANG Z L, WANG H L, 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): 9030.
[23] CHEN Y F, WANG K, NIE K Q,et al. Tuning the electronic structure of bimetallic CoCu clusters for efficient hydrolysis of ammonia borane. Chemical Engineering Journal, 2023, 451: 138931.
[24] DONG Y W, CHANG H H, LIU J H,et al. Open-structured CoCu-based nanosheets for catalytic hydrogen generation from ammonia borane hydrolysis. Journal of Physics and Chemistry of Solids, 2026, 209: 113290
[25] CAO Y Y, YANG S L, LIU Y T,et al. Chitosan-derived carbon aerogel stabilized Ru nanoparticles: facile fabrication and application in catalyzing NH₃BH₃ hydrolytic dehydrogenation. Fuel, 2026, 404: 136383.
[26] LI Z, HE T, LIU L,et al. Covalent triazine framework supported non-noble metal nanoparticles with superior activity for catalytic hydrolysis of ammonia borane: from mechanistic study to catalyst design. Chemical Science, 2017, 8(1): 781.
[27] WANG H L, WANG N, WANG L Y,et al. Hydrogen generation from formic acid boosted by functionalized graphene supported AuPd nanocatalysts. Journal of Inorganic Materials, 2022, 37(6): 547.
[28] CHEN X, JIN J R, LIU B,et al. Flexible and transparent leaf-vein electrodes fabricated by liquid film rupture self-assembly AgNWs for application of heaters and pressure sensors. Chemical Engineering Journal, 2024, 499: 156500.
[29] CHEN X X, ZHANG T, TIAN W J,et al. Solar-driven H₂O₂ production catalyzed by natural wood. ACS Catalysis, 2026, 16(2):1103.
[30] CUI Y H, SUN C N, HE Y X,et al. Boosting electrocatalytic nitrate reduction to ammonia on a hierarchical nanoporous Ag,Ni-codoped Cu catalyst via trimetallic synergistic and nanopore enrichment effects. Nano Letters, 2025, 25(2): 837.
[31] DING G P, HE Y X, ZHAO M,et al. Nanoporous surface high-entropy alloys enable tandem catalysis and ultrafast hydrogen spillover for efficient nitrate electroreduction to ammonia. Science China Chemistry, 2026, 69: 1233.
[32] FENG Z X, HE Y X, CUI Y H,et al. Efficient tandem electrocatalytic nitrate reduction to ammonia on bimodal nanoporous Ag/Ag-Co across broad nitrate concentrations. Nano Letters, 2024, 24(38): 11929.
[33] QU Y B, DAI T Y, DING G P,et al. Efficient tandem electrochemical reduction of nitrate to ammonia through coupling Co₂P with Co/Co₂P interface. Journal of Materials Science & Technology, 2026, 247: 226.
[34] SU X F, LI SF, PVP-stabilized Co-Ni nanoparticles as magnetically recyclable catalysts for hydrogen production from methanolysis of ammonia borane.International Journal of Hydrogen Energy, 2021, 46(27): 14384.
[35] DEKA J R, SAIKIA D, LU N F,et al. Bimetallic NiCo nanoparticles embedded in organic group functionalized mesoporous silica for efficient hydrogen production from ammonia borane hydrolysis. Nanomaterials,2024, 14(22): 1818
[36] CHEN M J, ZHANG D X, LI D,et al. All-around coating of CoNi nanoalloy using a hierarchically porous carbon derived from bimetallic MOFs for highly efficient hydrolytic dehydrogenation of ammonia-borane. New Journal of Chemistry, 2020, 44(7): 3021.
[37] 吴志杰. 能源转化催化原理. 中国石油大学出版社, 2022: 112-114.
[38] LIU K X, YANG S L, CHEN Y,et al. Enhanced catalytic behavior of h-BN supported CuNi bimetallic catalysts in hydrolytic dehydrogenation of NH₃BH₃. International Journal of Hydrogen Energy, 2022, 47(79): 33741.
[39] ZHANG X L, ZHANG D X, CHANG G G,et al. Bimetallic (Zn/Co) MOFs-derived highly dispersed metallic Co/HPC for completely hydrolytic dehydrogenation of ammonia-borane. Industrial & Engineering Chemistry Research, 2019, 58(17): 7209.
[40] CHANG L X, RAJAMANICKAM P, HSU L C,et al. Metal-organic framework-derived carbon-supported high-entropy alloy nanoparticles applied in ammonia borane hydrolytic dehydrogenation. Journal of Catalysis, 2024, 437: 115663.
[41] ZHAO B, LIU L, ZHOU D,et al. Probing the electronic structure of M-graphene oxide (M=Ni, Co, NiCo) catalysts for hydrolytic dehydrogenation of ammonia borane. Applied Surface Science, 2016, 362: 79.
[42] ZHANG W K, LIU J H, WANG J,et al. Construction of heterostructured CuO-Co₃O₄ catalyst for hydrogen evolution from ammonia borane hydrolysis. Journal of Physics and Chemistry of Solids, 2026, 208: 113037.
[43] ZHANG J R, JIA Y Q, CHU F,et al. Carbothermal shock fabrication of CoO-Cu₂O nanocomposites on N-doped porous carbon for enhanced hydrolysis of ammonia borane. Rare Metals, 2025, 44(8): 5486.
[44] MEHDI S, LIU Y Y, WEI H J, et al. P-induced Co-based interfacial catalysis on Ni foam for hydrogen generation from ammonia borane. Applied Catalysis B: Environmental, 2023, 325: 122317.
[45] NI Y W, HAN Z, LI W J,et al. Cobalt-promoted ruthenium catalysts on acidic zeolite for hydrogen production from ammonia borane hydrolysis. Chemical Engineering Journal, 2025, 521: 167130.
[46] XIONG C L, ZHANG X W, LEI Y T, et al. One-pot synthesis of ultrafine Ni_0.13Co_0.87P nanoparticles on halloysite nanotubes as efficient catalyst for hydrogen evolution from ammonia borane. Applied Clay Science, 2021, 214: 106293.
[47] WU HAN, LIU L L, LIU X Y,et al. In situ construction of Co-Mo₂C on N-doped carbon for efficient hydrogen evolution from ammonia borane hydrolysis. International Journal of Hydrogen Energy, 2025, 100: 330.
[48] LIU D, WANG H, ZHANG X W,et al. Amino pre‐coordination confinement‐induced PtCo Ordered Intermetallics with declined h₂o dissociation barrier for boosted ammonia borane hydrolysis. Energy & Environmental Materials, 2026, 9(1): e70113.