Advances in Copper-Based Catalysts for Hydrogen Production from Ammonia Borane Hydrolysis AITranslate

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［19］Lu Z H，Yao Q L，Zhang Z J，Yang Y W，Chen X S. Nanocatalysts for hydrogen generation from ammonia borane and hydrazine borane［J］.Journal of Nanomaterials，2014.

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［24］Chandra M，Xu Q. Room temperature hydrogen generation from aqueous ammonia-borane using noble metal nano-clusters as highly active catalysts［J］.Journal of Power Sources，2007，168（1）：135.

［25］Yang Y W，Feng G，Lu Z H，Hu N，Zhang F，Chen X S. In situ synthesis of reduced graphene oxide supported Co nanoparticles as efficient catalysts for hydrogen generation from NH3BH3［J］.Acta Physico-Chimica Sinica，2014，30：1180.

［26］Yao Q L，Shi W M，Feng G，Lu Z H，Zhang X L，Tao D J，Kong D J，Chen X S. Ultrafine Ru nanoparticles embedded in SiO2 nanospheres：highly efficient catalysts for hydrolytic dehydrogenation of ammonia borane ［J］. Journal of Power Sources，2014，257：293.

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［31］Akbayrak S，Erdek P，Özkar S. Hydroxyapatite supported ruthenium（0） nanoparticles catalyst in hydrolytic dehydrogenation of ammonia borane：insight to the nanoparticles formation and hydrogen evolution kinetics［J］.Applied Catalysis B：Environment and Energy，2013，142-143：187.

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Q Feng，J Li. Advances in electrocatalytic CO2 reduction with copper-based catalysts［J］.Nonferrous Metals Science and Engineering，2024，15（3）：364.

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［35］Kaya M，Zahmakiran M，Özkar S，Volkan M. Copper（0） nanoparticles supported on silica-coated cobalt ferrite magnetic particles：cost effective catalyst in the hydrolysis of ammonia-borane with an exceptional reusability performance［J］.ACS Applied Materials Interfaces，2012，4（8）：3866.

［36］（张楚宜，应宇哲，贾岩松，赵焯雅，李洋，施建峰. 电催化CO2还原反应铜基催化剂失效机理研究进展［J］.铜业工程，2024，（4）：30.）

C Y Zhang，Y Z Ying，Y S Jia，Z Y Zhao，Y Li，J F Shi. Research progress on deactivation mechanism of copper-based catalysts for electrocatalytic CO2 reduction reaction［J］.Copper Engineering，2024，（4）：30.

［37］Yao Q L，Chen X S，Lu Z H. Catalytic dehydrogenation of NH3BH3，N2H4，and N2H4BH3 for chemical hydrogen storage［J］.Energy and Environment Focus，2014，3：236.

［38］Umegaki T，Yan J M，Zhang X B，Shioyama H，Kuriyama N，Xu Q. Preparation and catalysis of poly （N-vinyl-2-pyrrolidone） （PVP） stabilized nickel catalyst for hydrolytic dehydrogenation of ammonia borane［J］.International Journal of Hydrogen Energy，2009，34（9）：3816.

［39］Staubitz A，Robertson A P，Manners I. Ammonia‐borane and related compounds as dihydrogen sources［J］.Chemistry Review，2010，110（7）：4079.

［40］Peng Y M，Zhang Y W，Guo A，Mao M Y，Wang Y，Long Y，Fan G Y. Universal low‐temperature oxidative thermal redispersion strategy for green and sustainable fabrication of oxygen‐rich carbons anchored metal nanoparticles for hydrogen evolution reactions［J］.Chemical Engineering Journal，2022，433（3）：133648.

［41］Cheng H F，Kamegawa T，Mori K，Yamashita H. Surfactant‐free nonaqueous synthesis of plasmonic molybdenum oxide nanosheets with enhanced catalytic activity for hydrogen generation from ammonia borane under visible light［J］.Angewandte Chemie International Edition，2014，126（11）：2910.

［42］Tong F X，Liang X Z，Wang Z Y，Liu Y Y，Wang P，Cheng H F，Dai Y，Zheng Z K，Huang B B. Probing the mechanism of plasmon‐enhanced ammonia borane methanolysis on a CuAg alloy at a single‐particle level［J］.ACS Catalysis，2021，11（17）：10814.

［43］Wang Y，Lv H，Grape E S，Gaggioli C A，Tayal A，Dharanipragada A，Willhammar T，Inge A K，Zou X D，Liu B，Huang Z H. A tunable multivariate metal-organic framework as a platform for designing photocatalysts［J］.  Journal of the American Chemical Society，2021，143（17）：6333.

［44］Wang L B，Li H L，Zhang W B，Zhao X，Qiu J X，Li A W，Zheng X S，Hu Z P，Si R，Zeng J. Supported rhodium catalysts for ammonia-borane hydrolysis：dependence of the catalytic activity on the highest occupied state of the single rhodium atoms［J］.Angewandte Chemie International Edition，2017，56（17）：4712.

［45］Gao Z，Wang G F，Lei T Y，Lv Z X，Xiong M，Wang L C，Xing S F，Ma J Y，Jiang Z，Qin Y. Enhanced hydrogen generation by reverse spillover effects over bicomponent catalysts［J］.Nature Communications，2022，13（1）：118.

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［47］Chen Y Z，Liang L，Yang Q，Hong M，Xu Q，Yu S H，Jiang H L. A seed‐mediated approach to the general and mild synthesis of non‐noble metal nanoparticles stabilized by a metal-organic framework for highly efficient catalysis［J］.Materials Horizons，2015，2（6）：606.

［48］Zhang S B，Li M，Li L S，Dushimimana F，Zhao J K，Wang S，Han J Y，Zhu X L，Liu X，Ge Q F，Wang H. Visible‐light‐driven multi-channel regulation of local electron density to accelerate activation of O-H and B-H bonds for ammonia borane hydrolysis［J］.ACS Catalysis，2020，10（24）：14903.

［49］Xu Q，Chandra M. Catalytic activities of non‐noble metals for hydrogen generation from aqueous ammonia‐borane at room temperature［J］.Journal of Power Sources，2006，163（1）：364.

［50］Yang X J，Cheng F Y，Tao Z L，Chen J. Hydrolytic dehydrogenation of ammonia borane catalyzed by carbon supported Co core-Pt shell nanoparticles［J］.Journal of Power Sources，2011，196（5）：2785.

［51］Lin Y X，Yang L，Jiang H L，Zhang Y K，Cao D F，Wu C Q，Zhang G B，Jiang J，Song L. Boosted reactivity of ammonia borane dehydrogenation over Ni/Ni2P heterostructure［J］.The Journal of Physical Chemistry Letters，2019，10（5）：1048.

［52］Li Z，He T，Liu L，Chen W D，Zhang M，Wu G T，Chen P. Covalent triazine framework supported non-noble metal nanoparticles with superior activity for catalytic hydrolysis of ammonia borane：from mechanistic study to catalyst design［J］.Chemical Science，2017，8（1）：781.

［53］Yamada Y，Yano K，Xu Q，Fukuzumi S. Cu/Co3O4 nanoparticles as catalysts for hydrogen evolution from ammonia borane by hydrolysis［J］.Journal of Physical Chemistry C，2010，114（39）：16456.

［54］Zhang J，Wang Y，Zhu Y M，Mi G，Du X G，Dong Y N. Shape‐selective fabrication of Cu nanostructures：Contrastive study of catalytic ability for hydrolytically releasing H2 from ammonia borane［J］.Renewable Energy，2018，118：146.

［55］Qiu X Q，Wu X，Wu Y W，Liu Q W，Huang C J. The release of hydrogen from ammonia borane over copper/hexagonal boron nitride composites［J］.RSC Advances，2016，6（108）：106211.

［56］Zahmakıran M，Durap F，Özkar S. Zeolite confined copper（0） nanoclusters as cost-effective and reusable catalyst in hydrogen generation from the hydrolysis of ammonia-borane［J］.International Journal of Hydrogen Energy，2010，35（1）：187.

［57］Ozay O，Inger E，Aktas N，Sahiner N. Hydrogen production from ammonia borane via hydrogel template synthesized Cu，Ni，Co composites［J］.International Journal of Hydrogen Energy，2011，36（14）：8209.

［58］Yang Y W，Lu Z H，Hu Y J，Zhang Z J，Shi W M，Chen X S，Wang T T. Facile in situ synthesis of copper nanoparticles supported on reduced graphene oxide for hydrolytic dehydrogenation of ammonia borane［J］.RSC Advances，2014，4（27）：13749.

［59］Yao Q L，Lu Z H，Zhang Z J，Chen X S，Lan Y Q. One‐pot synthesis of core‐shell Cu@SiO2 nanospheres and their catalysis for hydrolytic dehydrogenation of ammonia borane and hydrazine borane［J］.Scientific Reports，2014，4（1）：7597.

［60］Pachfule P，Yang X C，Zhu Q L，Tsumori N，Uchida T，Xu Q. From Ru nanoparticle-encapsulated metal-organic frameworks to highly catalytically active Cu/Ru nanoparticle-embedded porous carbon［J］.Journal of Materials Chemistry A，2017，5（10）：4835.

［61］Cao N，Hu K，Luo W，Cheng G Z. RuCu nanoparticles supported on graphene：a highly efficient catalyst for hydrolysis of ammonia borane［J］.Journal of Alloys and Compounds，2014，590：241.

［62］Huang X Y，Liu Y Y，Wen H，Shen R F，Mehdi S，Wu X L，Liang E J，Guo X J，Li B J. Ensemble-boosting effect of Ru-Cu alloy on catalytic activity towards hydrogen evolution in ammonia borane hydrolysis［J］.Applied Catalysis B：Environment and Energy，2021，287：119960.

［63］Zhao X R，Liu Y Y，Yuan H Y，Wen H，Zhang H H，Ashraf S M，Guan S Y，Liu T，Mehdi S，Shen R F，Guo X J，Fan Y P，Liu B Z，Li B J. Coupling atom ensemble and electron transfer in PdCu for superior catalytic kinetics in hydrogen generation［J］.Nano Research，2023，16（7）：9012.

［64］Zhou Y H，Cao X Y，Ning J Z，Ji C，Cheng Y，Gu J. Pd‐doped Cu nanoparticles vonfined by ZIF‐67@ZIF‐8 for efficient dehydrogenation of ammonia borane［J］.  International Journal of Hydrogen Energy，2023，45（56）：31440.

［65］Yang Y，Duan Y，Deng D，Li D，Sui D，Gao X. Cu@Pd/C with controllable Pd dispersion as a highly efficient catalyst for hydrogen evolution from ammonia borane［J］.Nanomaterials，2020，10（9）：1850.

［66］Güngörmez K，Metin Ö. Composition‐controlled catalysis of reduced graphene oxide supported CuPd alloy nanoparticles in the hydrolytic dehydrogenation of ammonia borane［J］.Applied Catalysis A：General，2015，494：22.

［67］Tian J J，Yang Y H，Lyu L Y，Xue Y，Wu K L，Shi Z H. Highly efficient hydrogen production via the hydrolysis of ammonia borane over nanostructured Pd‐Cu nanoparticles supported on PDA‐coated graphene［J］.ChemistrySelect，2022，7（35）：e202201632.

［68］Zhu Y M，Mao B L，Zhang J，Liu Q X，Li X，Song K X. Pt/Cu bimetallic stratiform nanocrystal cluster hierarchical frameworks：robust catalyst for hydrolyzing ammonia borane to generate hydrogen［J］.Advanced Materials Interfaces，2022，9（14）：2102478.

［69］Mao B L，Zhu Y M，Huang D H，Zhang J，Liu Q X，Li X，Song K X. Stepwise reduction and in situ loading of core‐shelled Pt@Cu nanocrystals on TiO2‐NTs for highly active hydrogen eolution［J］.Advanced Materials Interfaces，2023，10（6）：2201891.

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［76］Du Y S，Cao N，Yang L，Luo W，Cheng G Z. One-step synthesis of magnetically recyclable rGO supported Cu@Co core-shell nanoparticles：highly efficient catalysts for hydrolytic dehydrogenation of ammonia borane and methylamine borane［J］.New Journal of Chemistry，2013，37（10）：3035.

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［78］Xu W J，Liu M，Liu S L，Guan S Y，Zhang H H，Shen R F，Wang Y F，Li B J. A robust sandwich structural catalyst of （Cu/CuCo-MOF）2/MXene double heterojunction with outstanding activity toward hydrogen generation［J］.Applied Catalysis B：Environment and Energy，2024，358：12444.

［79］Wan C，Wang J P，Cheng D G，Chen F Q，Xu L X，Gao M B，Kang Y Q，Eguchi M，Yamauchi Y. Silica confinement for stable and magnetic Co-Cu alloy nanoparticles in nitrogen-doped carbon for enhanced hydrogen evolution［J］.Angewandte Chemie International Edition，2024，63（24）：e202404505.

［80］Wang Q J，Zou L L，Xu Q. Copper nanoparticles decorated on cobalt oxide nanosheets derived from bimetallic metal-organic-framework for hydrolysis of ammonia borane［J］.RSC Sustainability，2023，1（8）：1962.

［81］Yao Q L，Lu Z H，Wang Y Q，Chen X S，Feng G. Synergetic catalysis of non‐noble bimetallic Cu‐Co nanoparticles embedded in SiO2 nanospheres in hydrolytic dehydrogenation of ammonia borane［J］.Journal of Physical Chemistry C，2015，119（25）：4167.

［82］Chen Y F，Wang K，Nie K Q，Wang J O，Wang S F，Feng K，Zhong J. Tuning the electronic structure of bimetallic CoCu clusters for efficient hydrolysis of ammonia borane［J］.Chemical Engineering Journal，2023，451：138931.

［83］Song Y K，Gao C Y，Liu J H，Liu Z. Fabrication of multiatomic structure of Cu‐CoO/Co interface for efficient hydrogen generation from ammonia borane hydrolysis［J］.International Journal of Hydrogen Energy，2023，48（67）：26162.

［84］Liu J H，Li B，Dong Y W，Liu Q，Song Y K，Guo Y F，Zhao Y，Li X，Xiong J. Hydrolysis of ammonia borane for hydrogen generation on bimetallic CoCu catalysts：regulation of synergistic effect［J］.Catalysis Letters，2024，154（2）：461.

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［86］Deka J R，Diganta S K，Lu N F，Chen K T，Kao H M，Yang Y C. Space confined synthesis of highly dispersed bimetallic CoCu nanoparticles as effective catalysts for ammonia borane dehydrogenation and 4‐nitrophenol reduction［J］.Applied Surface Science，2021，538：148091.

［87］Zhang F M，Li R，Zhang J P，Dong H. KCC‐1 supported CuCo bimetal catalysts for promoting hydrogen production from ammonia borane hydrolysis［J］.Catalysis Letters，2022，152（9）：2832.

［88］Yang X，Li Q L，Li L L，Lin J，Yang X J，Yu C，Liu Z Y，Fang Y，Huang Y，Tang C C. CuCo binary metal nanoparticles supported on boron nitride nanofibers as highly efficient catalysts for hydrogen generation from hydrolysis of ammonia borane ［J］. Journal of Power Sources，2019，431：135.

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［93］Lu Z H，Li J P，Feng G，Yao Q L，Zhang F，Zhou R Y，Tao D J，Chen X S，Yu Z Q. Synergistic catalysis of MCM-41 immobilized Cu-Ni nanoparticles in hydrolytic dehydrogeneration of ammonia borane［J］.International Journal of Hydrogen Energy，2014，39（25）：13389.

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［95］Jiang R F，Yang M，Meng J K，Zhao P，Liu P，Zheng X C. Enhanced catalytic performance of CuNi bimetallic nanoparticles for hydrogen evolution from ammonia borane hydrolysis［J］.International Journal of Hydrogen Energy，2023，48（48）：18245.

［96］Liu K X，Yang S L，Chen Y，Zhang W L，Liu P，Zheng X C. Enhanced catalytic behavior of h-BN supported CuNi bimetallic catalysts in hydrolytic dehydrogenation of NH3BH3［J］.International Journal of Hydrogen Energy，2022，47（79）：33741.

［97］Li P，Chen R，Huang Y Q，Li W Q，Zhao S E，Tian S H. Activating transition metal via synergistic anomalous phase and doping engineering towards enhanced dehydrogenation of ammonia borane［J］.Applied Catalysis B：Environment and Energy，2022，300：120725.

［98］Gao D D，Zhang Y H，Zhou L Q，Yang K Z. CuNi NPs Supported on MIL‐101 as highly active catalysts for the hydrolysis of ammonia borane［J］.Applied Surface Science，2018，427：114.

［99］Xu W J，Liu M，Wang S F，Peng Z K，Shen R F，Li B J. Interfacial ensemble effect of copper nanoparticles and nickel metal‐organic framework on promoting hydrogen generation［J］.International Journal of Hydrogen Energy，2022，47（55）：23213.

［100］Wang C Y，Sun D D，Yu X F，Zhang X H，Lu Z M，Wang X X，Zhao J L，Li L L，Yang X J. Cu/Ni nanoparticles supported on TiO2（B） nanotubes as hydrogen generation photocatalysts via hydrolysis of ammonia borane［J］.Inorganic Chemistry Frontiers，2018，5（8）：2038.

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Basic Information:

DOI：10.13373/j.cnki.cjrm.XY25040004

Chinese Library Classification Number:O643.3

Citation Information:

Hydrogen, as a key clean energy source, is essential for global energy transition and carbon neutrality. Nevertheless, challenges associated with its safe and efficient storage and transportation hinder large-scale implementation. Among various hydrogen carriers, ammonia borane (NH₃BH₃, AB) stands out as a promising candidate due to its exceptional hydrogen storage capacity (19.6%), ambient stability, and mild hydrolysis conditions. While catalytic hydrolysis of AB offers a sustainable route to hydrogen generation under mild conditions, the reliance on costly noble metal catalysts has driven research into cost-effective alternatives. Copper-based catalysts have attracted significant interest as attractive alternatives to noble metal catalysts due to their intrinsic catalytic activity, cost-effectiveness, and earth abundance. This review systematically examined recent advances in copper-based catalysts, focusing on three key aspects：AB hydrolysis mechanism, catalyst synthesis strategies and structure-activity relationships, and AB byproduct recycling and regeneration. AB hydrolysis, fundamentally involving the synergistic activation of B–H and O–H bonds, proceeded via a complex mechanism where water dissociation (O–H bond cleavage) was identified as the rate-determining step. This review comprehensively analyzed various catalyst systems, ranging from copper monometallic catalysts to bimetallic, trimetallic, polymetallic, and copper-based oxides, as well as other types such as borides and phosphides. Early studies demonstrated that support-free Cu nanoparticles (NPs) showed low activity while supported-Cu nanoparticles exhibited an enhanced activity. Among them, reduced graphene oxide-supported Cu NPs (Cu/RGO) showed a highly efficient activity toward AB hydrolysis due to the strong interaction between metal NPs and support. The core-shell structured (e.g., Cu@SiO₂) showed a good catalytic activity and superior reusability due to the active site protected by the porous shell. Compared to monometallic systems, Cu-based heterometallic catalysts exhibited significant advantages in catalytic activity and stability, which was due to the synergistic effects between copper and other metals. A series of Cu-based noble and non-noble heterometallic catalysts had been synthesized and applied in AB hydrolysis for hydrogen generation. Noble metal catalysts possessed unique electronic structures and surface properties that enable effective adsorption and activation of AB and water molecules, thereby reducing activation energy and accelerating hydrolysis kinetics. Combining Cu with noble metals could take the advantage of the high activity of noble metals and the cost advantages of Cu. For example, RuCu, PdCu, and PtCu alloys a better catalytic activity than their corresponding monometallic catalysts. Noble metal-containing Cu-based catalysts indicated efficient catalytic performance toward AB hydrolysis reaction, but it was important to search the cheap and efficient noble-metal free catalysts from the perspective of industrial applications. The optimal CuFe, Cu@Co-MOF, and CuNi/g-C₃N₄ catalyst displayed excellent catalytic performance. Compared to their bimetallic and monometallic counterparts, CuNiCo and CuCoMo trimetallic catalysts displayed superior catalytic activity. Polymetallic catalysts derived from high-entropy alloys offered broad compositional tunability and exceptional stability, making them promising candidates for future research. MnFeCoNiCu high-entropy alloys showed a good structural stability but require further activity optimization. Due to the high oxidation rate of non-precious metal NPs, the direct use of non-precious metal oxides as catalyst of AB hydrolysis had received much attention. For example, CuCo₂O₄ with oxygen vacancies demonstrated enhanced catalytic activity due to the increased density of active sites and improved electron mobility. The dynamic state of oxides (potential reduction during reaction) and the precise role of vacancies required deeper investigation. Cu-based boride and phosphide catalysts displayed enhanced catalytic performance, however, the intrinsic active sites of these catalysts and their stability under practical conditions needed further clarification. To facilitate the widespread adoption of AB as a liquid-phase hydrogen storage material, there was an urgent need to develop cost-effective recycling technologies to achieve efficient and sustainable AB regeneration from its hydrolysis borate byproducts. Several efficient routes for the regeneration of AB had been established. Copper-based catalysts demonstrated significant potential for efficient and cost-effective hydrogen generation from AB hydrolysis. However, significant challenges remained in advancing hydrogen production via AB hydrolysis, warranting further investigation：1) exploring single-atom or fully-exposed cluster Cu catalysts to maximize metal atom utilization；2) designing high-entropy alloys to enhance both catalytic activity and stability；3) employing in-situ/operando characterization techniques and density functional theory (DFT) calculations to deepen understanding, particularly concerning active site dynamics and the roles of vacancies and oxidized states；4) developing cost-effective and scalable pathways for the regeneration of AB hydrolysis byproducts；5) coupling AB hydrolysis directly with downstream hydrogen applications (e.g., fuel cells, hydrogenation processes)；6) applying artificial intelligence (AI) for accelerated catalyst design and system optimization. Overcoming limitations in intrinsic catalyst activity, long-term stability under operational conditions, and system integration complexity was essential for realizing AB as a practical hydrogen carrier to enable portable and distributed clean energy systems.