Chemical Hydrogen Storage Materials Research Articles

Ternary Fe–Ni–B particles supported on Cu(OH)2–Cu foam: A highly efficient and stable catalyst for hydrolysis of ammonia borane

Ammonia borane (NH3BH3) as a solid chemical hydrogen storage material with a high hydrogen content can be hydrolyzed under mild conditions to release hydrogen. In this work, Fe–Ni–B/Cu(OH)2–Cu foam was synthesized by combining in situ growth and electroless plating. Compared with the binary Fe–B/Cu(OH)2–Cu foam and Ni–B/Cu(OH)2–Cu foam prepared by the same method, the ternary Fe–Ni–B/Cu(OH)2–Cu foam has superior catalytic performance. The Fe–Ni–B/Cu(OH)2–Cu foam catalyst was able to achieve a maximum hydrogen production rate of 5.6 ml min−1 cm−2 at 298 K with an activation energy as low as 46.3 kJ mol−1. And more importantly, its catalytic efficiency has hardly decayed after ten cycles. These excellent properties are due to its low activation energy and the large specific surface, multi–site Cu(OH)2–Cu–foam carrier.

Hydrogen production from chemical hydrogen storage materials over copper‐based catalysts

AbstractHydrogen, as a clean and efficient energy source, is one of the important energy carriers in the future. However, the safe storage and delivery of hydrogen is still a bottleneck in its practical applications. Chemical hydrides (such as NaBH4, NH3BH3, N2H4·H2O, N2H4BH3, and HCOOH) are considered as potential chemical hydrogen storage materials that can achieve rapid on‐site hydrogen production. At present, the most critical issue for them is to develop economic catalysts to achieve efficient hydrogen production from chemical hydrides. Copper (Cu) is considered as a promising catalyst that is one of the most reactive metals among the first‐row transition metals and economically cheap. In this review, we outline the recent advancements of Cu‐based catalysts in catalyzing hydrogen production from chemical hydrides. Moreover, the synthesis methods, characterization techniques, and hydrogen production catalytic activity of Cu‐based catalysts were also introduced. Finally, a brief conclusion and outlook are given for the application of Cu‐based catalysts in the dehydrogenation of chemical hydrides. We hope that this review will stimulate interest in the promising research area of Cu‐based catalysts for the dehydrogenation of chemical hydrides.

Cobalt Phosphide-Supported Single-Atom Pt Catalysts for Efficient and Stable Hydrogen Generation from Ammonia Borane Hydrolysis.

Ammonia borane (AB) has emerged as a promising chemical hydrogen storage material. The development of efficient, stable, and cost-effective catalysts for AB hydrolysis is the key to achieving hydrogen energy economy. Here, cobalt phosphide (CoP) is used to anchor single-atom Pt species, acting as robust catalysts for hydrogen generation from AB hydrolysis. Thanks to the high Pt utilization and the synergy between CoP and Pt species, the optimized Pt/CoP-100 catalyst exhibits an unprecedented hydrogen generation rate, giving a record turnover frequency (TOF) value of 39911 and turnover number of 2926829 at room temperature. These metrics surpass those of all existing state-of-the-art supported metal catalysts by an order of magnitude. Density functional theory calculations reveal that the integration of single-atom Pt onto the CoP substrate significantly enhances adsorption and dissociation processes for both water and AB molecules, thereby facilitating hydrogen production from AB hydrolysis. Interestingly, the TOF value is further elevated to 54878 under UV-vis light irradiation, which can be attributed to the efficient separation and mobility of photogenerated carriers at the Pt-CoP interface. The findings underscore the effectiveness of CoP as a support for single-atom metals in hydrogen production, offering insights for designing high-performance catalysts for chemical hydrogen storage.

Chemical material as a hydrogen energy carrier: A review

In light of climate change imperatives, there arises a critical need for technological advancements and research endeavors towards clean energy alternatives to replace conventional fossil fuels. Additionally, the development of high-capacity energy storage solutions for global transportability becomes paramount. Hydrogen emerges as a promising environmentally sustainable energy carrier, devoid of carbon dioxide emissions and possessing a high energy density per unit mass. Its versatile applicability spans various sectors including industry, power generation, and transportation. However, the commercialization of hydrogen necessitates further technological innovations. Notably, high-pressure compression for hydrogen storage presents safety challenges and inherent limitations in storage capacity about 30%–50% lost production of hydrogen. Consequently, substantial research endeavors are underway in the domain of material-based chemical hydrogen storage that reactions to occur at temperatures below 200 ℃. This approach enables the utilization of existing infrastructure, such as fossil fuels and natural gas, while offering comparatively elevated hydrogen storage capacities. This study aims to introduce recent investigations concerning the synthesis and decomposition mechanisms of chemical hydrogen storage materials, including methanol, ammonia, and Liquid Organic Hydrogen Carrier (LOHC).

Desirable performance and mechanism of RuPd nanoalloys in catalyzing hydrolytic dehydrogenation of NH3BH3

The dehydrogenation of liquid-phase chemical hydrogen storage materials (such as ammonia borane, AB, NH3BH3) is a promising strategy to develop the promising hydrogen economy. Considering that the self-hydrolysis of AB is nearly impossible at room temperature, it is very worthwhile to search a robust catalyst for this hydrolytic reaction and clarify the catalytic mechanism. In this work, a glucose-derived N/O co-doped and multi-level porous carbon (marked as g-pC, SBET = 1356 m2 g−1, Vtotal = 0.762 cm3 g−1, Smicro = 1079 m2 g−1, Vmicro = 0.427 cm3 g−1) is prepared for confining RuPd alloys. Benefitting from the positive effect of g-pC (such as the particular anchoring and geometric effects on highly and tightly confining RuPd nanoparticles, as well as enhanced hydrophilicity) and the exceptional metal alloy effect, the obtained bimetallic catalysts unveil drastically enhanced catalytic activity in AB hydrolysis compared to the monometallic counterparts. Especially, catalyzed by the optimal Ru0.25Pd0.75@g-pC with a mean alloy size of 1.5 nm (10 mg), the dehydrogenation of 1.00 mmol AB can be finished within 1 min at 303 K in NaOH solution (1.5 M). The corresponding turnover frequency and hydrogen generation rate are calculated to be 541.09 min−1 and 145,950 mL min−1 g−1, respectively. Moreover, about 62% of the initial catalytic activity is still retained even in the 18th cyclic experiment, suggesting the extraordinarily long durability. In addition, the isotopic analyses present a kinetic isotope effect (KIE) of 3.38, further confirming that the scission of an O-H bond in H2O is the rate-controlling step in this hydrolytic reaction. Our work offers a competitive metal alloy catalyst for generating hydrogen from AB aqueous solution and promote the development and safety utilization of hydrogen energy.

Thermodynamic evaluations of the acceptorless dehydrogenation and hydrogenation of pre-aromatic and aromatic N-heterocycles in acetonitrile.

N-heterocycles are important chemical hydrogen-storage materials, and the acceptorless dehydrogenation and hydrogenation of N-heterocycles as organic hydrogen carriers have been widely studied, with the main focus on the catalyst synthesis and design, investigation of the redox mechanisms, and extension of substrate scope. In this work, the Gibbs free energies of the dehydrogenation of pre-aromatic N-heterocycles (YH2) and the hydrogenation of aromatic N-heterocycles (Y), i.e., ΔGH2R(YH2) and ΔGH2A(Y), were derived by constructing thermodynamic cycles using Hess' law. The thermodynamic abilities for the acceptorless dehydrogenation and hydrogenation of 78 pre-aromatic N-heterocycles (YH2) and related 78 aromatic N-heterocycles (Y) were well evaluated and discussed in acetonitrile. Moreover, the applications of the two thermodynamic parameters in identifying pre-aromatic N-heterocycles possessing reversible dehydrogenation and hydrogenation properties and the selection of the pre-aromatic N-heterocyclic hydrogen reductants in catalytic hydrogenation were considered and are discussed in detail. Undoubtedly, this work focuses on two new thermodynamic parameters of pre-aromatic and aromatic N-heterocycles, namely ΔGH2R(YH2) and ΔGH2A(Y), which are important supplements to our previous work to offer precise insights into the chemical hydrogen storage and hydrogenation reactions of pre-aromatic and aromatic N-heterocycles.

Rh0.7Ru0.3-MoOx supported on carbon nanotubes boosts hydrogen generation from hydrazine borane at room temperature

Hydrazine borane (HB, N2H4BH3) is gaining attention as a promising chemical hydrogen storage material due to its impressive hydrogen capacity (15.4 wt%) and stability under normal conditions. However, its dehydrogenation properties have remained unsatisfactory despite numerous efforts. In this study, we have successfully developed rhodium-ruthenium nanoparticles modified with MoOx and supported on carbon nanotubes (Rh0.7Ru0.3-MoOx/CNTS) using a facile co-reduction method. Surprisingly, the Rh0.7Ru0.3-MoOx/CNTS catalyst exhibits outstanding performance, surpassing all previously reported activities for HB dehydrogenation. It demonstrates a high turnover frequency (TOF) value of 4412 h−1 at 303 K, 100 % selective conversion of hydrogen, and excellent stability. Through XPS, TEM, BET, and XRD analysis, we have determined that the exceptional performance of Rh0.7Ru0.3-MoOx/CNTS can be attributed to the synergistic effect of CNTS and MoOx on the catalyst's electronic structure, crystal structure, and particle size. These results provide a solid foundation for the potential application of HB in hydrogen fuel cells.

Interfacial synergy between Pt3Co nanoparticles and CoO for efficient ammonia borane hydrolysis

Ammonia borane (AB, NH3BH3) with the high H2 content has been regarded as a promising material for chemical hydrogen storage. AB can hydrolyze to release H2 under the catalysis of noble-metal catalysts with high activity, but the high cost of noble-metals and their poor long-term stability prohibit the large-scale applications. Developing more cost-effective and stable catalysts by introducing cheap transition metal elements has been a promising strategy. Herein, we adopted a step-by-step precipitation method to synthesize bimetallic Pt-Co catalysts supported on rutile TiO2, which show significantly improved performance in AB hydrolysis reaction. The optimized 0.9Pt3.5Co/TiO2 catalyst (with the Pt and Co loadings of 0.9 and 3.5 wt%, respectively) exhibits an extremely high H2 generation rate, showing a turnover frequency value of 2163 molH2 molPt-1 min−1 at 298 K, 9 times higher than that of 0.9Pt/TiO2 catalyst and superior to those of most of the reported Pt-based catalysts. Structure characterizations and theoretical calculations reveal that the promoted AB hydrolysis performance arises from the interfacial synergistic effect between the supported Pt3Co alloy and cobalt oxide CoO, which accelerates the B-H bond cleavage and water activation, respectively. The excellent AB hydrolysis performance of the Pt-Co catalysts indicates the great prospects of alloy-oxide interfaces in the field of liquid phase chemical hydrogen storage.

Unveiling the bifunctional modulation evoked by bromine doping of CoP towards efficient hydrolytic hydrogen generation

Developing efficient and economical catalysts for hydrolytic hydrogen production from chemical hydrogen storage materials such as ammonia borane and NaBH4 is highly desirable but challenging. Herein, Br doped CoP nanoparticles in a carbon−based polyhedron with controllable morphology were developed as such an efficient hydrogen generation catalyst, and the bifunctional modulation of Br doping was explored. Firstly, regulating the doping content of Br results in the formation of more and larger nanopores in the CoP polyhedron, exposing more accessible active sites. Secondly, Co vacancies are introduced via Br doping, which significantly optimizes the electronic structure of Co atom, thus boosting AB and water dissociation, i.e., the rate−determining step (RDS). Therefore, the Br1 −CoP@C catalyst with optimal composition exhibited a superb turnover frequency (TOF) of 67.3 min−1, implying an astonishing over 3 −fold improvement compared with CoP@C. These findings showcase a novel and promising approach to build high−efficiency nanocatalysts for hydrogen production and beyond.

Porous silica supported Ag core-Pd shell composite: Seed-mediated stepwise reduction and tunable dispersion for boosting catalytic hydrogen evolution

For developing efficient and practical catalysts to achieve controllable hydrogen evolution from chemical hydrogen storage material, we herein demonstrate a seed-mediated stepwise reduction and tunable dispersion protocol to fabricate porous silica supported Ag core - Pd shell composites (Pd@Ag/SiO2) with serial metal molar ratios. By reasonable regulation for reduction sequence and growing conditions, the Pd@Ag bimetal layered nanostructure could be piloted to take orderly shape; via adjusting addition time and dosage for the reactants and additives, the resultant Pd@Ag nanoagents can be firmly attached on porous silica. The little by little assembled nanoagents with mean size of 10 nm on the silica microspheres construct a loose and porous secondary microstructure, leading to increment of specific surface area to some degrees. The generation of electron synergistic effect among the metals and carrier, verified by the XPS analysis, contributes to boosting the catalytic ability. The catalytic activity of the bimetal composites all exceed that of mono-metal composites, of which the bimetal composite Pd0.75@Ag0.25/SiO2 holds the top catalytic ability, even beyond that of Pd/SiO2 or Pd-NPs, followed by Pd0.5@Ag0.5/SiO2 and Pd0.25@Ag0.75/SiO2. The AB hydrolysis catalyzed by Pd0.75@Ag0.25/SiO2 at the given temperatures (293 to 313 K) is validated to be a first-order reaction, with apparent activation energy of 42.46 kJ·mol−1 and TOF value of 109.99 min−1. The catalyst Pd0.75@Ag0.25/SiO2 presents satisfactory stability, still retaining 83.2 % initial catalytic activity after five repeated use.

Preparation of rice husk-based carbon supported ruthenium catalyst for the hydrolysis of ammonia borane to produce hydrogen

An efficient dehydrogenation catalyst is crucial for the application of ammonia borane (NH3BH3, AB) as a solid chemical hydrogen storage material. In this work, a kind of nitrogen-doped rice husk activated carbon (N-RHC) was prepared by roasting melamine and rice husk at high temperature under nitrogen atmosphere. With N-RHC as the support, the rice husk-based carbon supported ruthenium catalyst (Ru/N-RHC) was prepared through impregnation with the RuCl3 solution and its catalytic performance in the hydrolysis of ammonia borane to produce hydrogen was investigated. The results indicate that the Ru/N-RHC catalyst with a Ru loading of 5% performs excellently in the hydrolysis of ammonia borane; the reaction turnover frequency (TOF) reaches 83.71 min−1 and the apparent activation energy decreases from 88.9 to 64.9 kJ/mol under light irradiation. In addition, the hydrogen production rate is positively correlated with the content of ammonia borane and catalyst.

Surfactant-assisted fabrication of prussian blue analogs as bifunctional electrocatalysts for water and hydrazine oxidation

The development of multifunctional catalysts for sustainable and proficient utilization of chemical energy is the utmost demand of the time. Water and hydrazine are auspicious energy carriers because of their high hydrogen content and henceforth can be employed as chemical hydrogen storage materials or as fuels for the direct fuel cells. In the present study, cationic surfactant-assisted Prussian blue analogs (PBAs) i.e., Mx[Fe(CN)5(N2C6H4)]·yC19H34NBr abbreviated as SF[Fe-CNPy-M]; SF = N-tridecyl-3-methylpyridinium bromide and M = manganese (Mn), cobalt (Co) and nickel (Ni), are synthesized and utilized as bifunctional heterogeneous OER and HzOR electrocatalysts under mild reaction conditions. The synthesis of electrocatalysts is confirmed by spectroscopic techniques i.e., Fourier transforms infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX) analysis, and X-ray photoelectron spectroscopy (XPS). The electrochemical measurements reveal an increase in current density, electrochemical surface area and catalytic stability compared to the reported PBAs for OER and HzOR. Among all the synthesized PBAs, SF[Fe-CNPy-Co] displays better electrochemical activity towards OER with 101 mV·dec−1 Tafel slope and appreciably low overpotential value of 470 mV to attain the current density of 10 mA.cm−2. SF[Fe-CNPy-Co] is further tested for HzOR and the results show that it exhibits high activity with the diffusion coefficient of 3.55 × 10−6 cm2.s−1 and rate constant of 3.411× 10−4 cm.s−1. This work proposes a pristine pathway to formulate efficient bifunctional electrocatalysts employing surfactant-assisted pentacyanoferrates-based PBAs for OER and HzOR.

Integration of the PEMFC with a hydrogen production device adopting sodium borohydride and metal cobalt catalyst

Hydrolysis technology that releases hydrogen from chemical hydrogen storage materials is a method to produce hydrogen. Hydrogen storage has excellent development potential and is also one of the sources of large amounts of hydrogen. A sodium borohydride hydrogen production experiment was carried out based on steam hydrolysis technology. The system reaction tank is divided into a water-carrying bed and a catalyst bed. A mixed aqueous solution with a concentration of 1 wt% sodium hydroxide (NaOH) + 10 wt% sodium borohydride (NaBH4) was used for the hydrogen production reaction test. These experiments determined the appropriate aqueous solution and water vapor combination, and optimal parameters for hydrogen production. The hydrogen production catalyst powder, blend ratio, different steel ball ratios, and ball milling time at the steam hydrogen production end will all affect the powder's fineness and hydrogen production stability. Under catalyst temperature control, the by-products solidify at a specific temperature, which affects the gas passage and causes blockage. Increasing the hydrogen production in an aqueous solution requires a Co2+/Al2O3 catalyst, or a temperature control method to catalyze hydrogen production to obtain stable hydrogen production suitable for emergencies without hydrogen storage containers. This experiment built a hydrogen production system combined with a fuel cell for power generation testing. The test process and results indicate whether the aqueous solution and steam technology can be an effective solution when the hydrolysis hydrogen production technology is matched.

Mechanistic insight into efficient H2 generation upon HCOONa hydrolysis

Sodium formate (SF) is regarded as a technological additive to improve H2 generation upon HCOOH dehydrogenation. The development of SF as a hydrogen storage material is still a challenge. Herein, we report the design and synthesis of carbon nanosphere-stabilized Pd nanoparticles (Pd/CNS) for the direct H2 generation upon SF hydrolysis in the presence of Fe3+. The tandem reaction, isotopic mass spectrometry, and gas chromatograms result confirmed that SF hydrolysis generates H2 with one H atom provided by SF and other H by H2O. The kinetic study and detailed mechanistic investigations have demonstrated that the concerted process between the cleavage of O-H bond in H2O and -O2C-H bond oxidative addition is the rate-controlling step in SF hydrolysis. This work offers a new chemical hydrogen storage material (HCOONa) for the high-efficiency generation, transport, and storage of H2.

CuCo2O4–NiO heterostructure catalysts for hydrogen production from ammonia borane

Ammonia borane (NH3BH3, AB) has been considered as one of the most attractive candidates for chemical hydrogen-storage materials and chemical hydrogen generation materials. Development of low-cost and high-performance catalysts for hydrogen generation from AB is highly desirable, which is still a huge challenge. Hollow sphere CuCo2O4 promotes the catalytic hydrolysis of AB due to its unique hollow sphere shape and the synergistic effect of Co and Cu elements. In this study, a heterogeneous structured catalyst containing NiO and CuCo2O4 was developed by a simple and low-cost method in order to improve the catalytic performance of CuCo2O4. Initially, CuCo2O4 with hollow sphere structure was synthesized by hydrothermal method, and then NiO were deposited onto CuCo2O4 by impregnation-calcination method to form a heterogeneous structure. The CuCo2O4–NiO catalyst showed good catalytic activity for the hydrolysis of AB. The catalytic performance of CuCo2O4–NiO was then optimised by controlling the concentration of the impregnated salt solution, and the optimised catalytic performance was 1.42 times that of pure CuCo2O4 with a HER value of 870 mLH2gcat−1min−1. This low-cost CuCo2O4–NiO obtained by impregnation-calcination method is valuable for catalytic hydrogen production from AB.

Cobalt-Promoted Noble-Metal Catalysts for Efficient Hydrogen Generation from Ammonia Borane Hydrolysis.

Ammonia borane (AB) has been regarded as a promising material for chemical hydrogen storage. However, the development of efficient, cost-effective, and stable catalysts for H2 generation from AB hydrolysis remains a bottleneck for realizing its practical application. Herein, a step-by-step reduction strategy has been developed to synthesize a series of bimetallic species with small sizes and high dispersions onto various metal oxide supports. Superior to other non-noble metal species, the introduction of Co species can remarkably and universally promote the catalytic activity of various noble metals (e.g., Pt, Rh, Ru, and Pd) in AB hydrolysis reactions. The optimized Pt0.1%Co3%/TiO2 catalyst exhibits a superhigh H2 generation rate from AB hydrolysis, showing a turnover frequency (TOF) value of 2250 molH2 molPt-1 min-1 at 298 K. Such a TOF value is about 10 and 15 times higher than that of the monometal Pt/TiO2 and commercial Pt/C catalysts, respectively. The density functional theory (DFT) calculation reveals that the synergy between Pt and CoO species can remarkably promote the chemisorption and dissociation of water molecules, accelerating the H2 evolution from AB hydrolysis. Significantly, the representative Pt0.25%Co3%/TiO2 catalyst exhibits excellent stability, achieving a record-high turnover number of up to 215,236 at room temperature. The excellent catalytic performance, superior stability, and low cost of the designed catalysts create new prospects for their practical application in chemical hydrogen storage.

Nanosizing Approach-A Case Study on the Thermal Decomposition of Hydrazine Borane.

Hydrazine borane (HB) is a chemical hydrogen storage material with high gravimetric hydrogen density of 15.4 wt%, containing both protic and hydridic hydrogen. However, its limitation is the formation of unfavorable gaseous by-products, such as hydrazine (N2H4) and ammonia (NH3), which are poisons to fuel cell catalyst, upon pyrolysis. Previous studies proved that confinement of ammonia borane (AB) greatly improved the dehydrogenation kinetics and thermodynamics. They function by reducing the particle size of AB and establishing bonds between silica functional groups and AB molecules. In current study, we employed the same strategy using MCM-41 and silica aerogel to investigate the effect of nanosizing towards the hydrogen storage properties of HB. Different loading of HB to the porous supports were investigated and optimized. The optimized loading of HB in MCM-41 and silica aerogel was 1:1 and 0.25:1, respectively. Both confined samples demonstrated great suppression of melting induced sample foaming. However, by-products formation was enhanced over dehydrogenation in an open system decomposition owing to the presence of extensive Si-O···BH3(HB) coordination that further promote the B-N bond cleavage to release N2H4. The Si-OH···N(N2H4) hydrogen bonding may further promote N-N bond cleavage in the resulting N2H4, facilitating the formation of NH3. As temperature increases, the remaining N-N-B oligomeric chains in the porous silica, which are lacking the long-range structure may further undergo intramolecular B-N or N-N cleavage to release substantial amount of N2H4 or NH3. Besides open system decomposition, we also reported a closed system decomposition where complete utilization of the N-H from the released N2H4 and NH3 in the secondary reaction can be achieved, releasing mainly hydrogen upon being heated up to high temperatures. Nanosizing of HB particles via PMMA encapsulation was also attempted. Despite the ester functional group that may favor multiple coordination with HB molecules, these interactions did not impart significant change towards the decomposition of HB selectively towards dehydrogenation.

Anomalous metastable hcp Ni nanocatalyst induced by non-metal N doping enables promoted ammonia borane dehydrogenation

Developing high-performing non-noble transition metal catalysts for H2 evolution from chemical hydrogen storage materials is of great significance for the hydrogen economy system, yet challenging. Herein, we present for the first time that anomalous metastable hexagonal close-packed Ni nanoparticles induced by heteroatom N doping encapsulated in carbon (N-hcp-Ni/C) can exhibit admirable catalytic performance for ammonia borane (AB) dehydrogenation, prominently outperforming conventional fcc Ni counterpart with similar morphology and favorably presenting the state-of-the-art level. Comprehensive experimental and theoretical studies unravel that unusual hcp phase engineering of Ni together with N doping could induce charge redistribution and modulate electronic structure, thereby facilitating H2O adsorption and expediting H2O dissociation (rate-determining step). As a result, AB dehydrogenation can be substantially boosted with the assistance of N-hcp-Ni/C. Our proposed strategy highlights that unconventional crystal phase engineering coupled with non-metal heteroatom doping is a promising avenue to construct advanced transition metal catalysts for future renewable energy technologies.

In situ encapsulating cobalt phosphide into a quasi-MOF: a high-performance catalyst for hydrolytic dehydrogenation of ammonia borane

The development of efficient, durable and economical catalysts based on non-precious metals for the controllable and fast hydrogen evolution from chemical hydrogen storage materials is highly desirable for the hydrogen economy.

Cation/anion-doping induced electronic structure regulation strategy to boost the catalytic hydrogen evolution from ammonia borane hydrolysis

Exploration of high-performance and cost-effective catalysts for hydrogen production from chemical hydrogen-storage materials is vital but still a challenge. Herein we report the synthesis of a ZIF-67 derived Co3O4 nanoparticles in a carbon-based nanoframeworks and discover that doping phosphorus into Co3O4 has a unique electronic structure modulation effect, resulting in a nearly 29-fold enhancement of the catalytic activity for ammonia borane hydrolytic dehydrogenation. Furthermore, combining the P doping with Cu doping, a strong synergistic effect is realized to boost the catalytic H2 generation with an astonishing nearly 51-fold improvement (turnover frequency, TOF = 35.6 min−1). Based on the experimental and theoretical results, the enhanced performance is attributed to the optimization of the electronic configuration and the downshift of d-band center over Co3O4 after P/Cu doping, thereby facilitating H2O dissociation and hydrogen desorption. This work will be applicable to designing other metal based nanocatalysts toward more efficient energy conversion reactions.