Hierarchical porous CuNi-based bimetal-organic frameworks as efficient catalysts for ammonia borane hydrolysis

doi:10.1016/j.catcom.2020.106057

Catalysis Communications

Volume 143, 5 August 2020, 106057

https://doi.org/10.1016/j.catcom.2020.106057 Get rights and content

Highlights

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CuNi-MOFs with a hierarchical porous structure are facilely fabricated.
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The isolated Cu and Ni endow the catalysts outstanding single-atom activity.
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They exhibit superior catalytic performance for AB hydrolysis.

Abstract

Ammonia borane (NH₃BH₃, AB) hydrolysis is an effective strategy to utilize hydrogen energy. In this work, the hierarchical porous CuNi bimetal-organic frameworks (CuNi-MOFs) are fabricated through a facile solvothermal method and characterized by various techniques. The CuNi-MOFs display outstanding catalytic activity and remarkable durability for the hydrolytic dehydrogenation of AB. The corresponding turnover frequency reaches 40.85 mol_H2 · mol_Metal⁻¹ · min⁻¹ and the apparent activation energy (28.99 kJ mol⁻¹) is lower than those of many catalysts previously reported. The results verify the resultant CuNi-MOFs are promising for the hydrolysis of hydrogen storage materials.

Graphical abstract

Introduction

As a renewable non-toxic, clean, environmentally benign and abundant energy source with high chemical energy density (142 MJ kg⁻¹), hydrogen is considered to be a promising candidate who could replace traditional fossil fuels with limited reserves, addressing the challenges of increasing energy demands and environmental pollutions [1]. However, the problem related to hydrogen storage is one of the most severe issues, which restricts the practical applications of the hydrogen and the foreseeable hydrogen economy. Therefore, it is necessary to focus on suitable hydrogen storage materials. So far, ammonia borane (NH₃-BH₃, AB) has become one of the ideal hydrogen storage materials due to its low molecular weight, zero toxicity, high hydrogen storage density (19.6 wt%), high stability, high solubility and high hydrolysis efficiency in water at room temperature [2]. Literature has reported that the hydrolysis is an effective way to generate hydrogen from AB catalyzed by proper catalyst (Eq. (1)). Interestingly, non-noble transition metals, as well as their binary or ternary alloys or compounds, have been developed as catalysts for AB hydrolysis [[3], [4], [5]]. In particular, for the catalysts, it is necessary to highly disperse the metallic nanoparticles since their agglomeration facilitates the masking of active sites and thereby impairs their catalytic performance. ${NH}_{3} {BH}_{3} + 2 H_{2} O \overset{catalyst}{\to} {NH}_{4} {BO}_{2} + 3 H_{2}$

As a new class of crystalline porous materials, metal-organic frameworks (MOFs), also known as coordination networks or coordination polymers, are composed of inorganic clusters bridged by organic ligands and possess advantages of both inorganic and organic porous compositions, endowing them unique characteristics such as tunable pore size, high accessible surface area, open metal site and well-defined structure [6,7]. Therefore, MOFs have attracted tremendous research interest for their potential applications including in the field of catalysis [[8], [9], [10]]. Particularly, copper- and nickel-based MOFs exhibit high activity in many catalytic reactions due to their unsaturated metal sites. For example, Ansari et al. [11] found the lactam functionalized Cu-MOFs exhibited fascinating activity for the conversion of CO₂ to cyclic carbonates under mild conditions. Huang et al. [12] successfully applied porous Cu-MOFs as catalysts for wet peroxide oxidation of phenol. Yang et al. [13] studied the catalytic decarboxylation of oleic acid to n-heptadecane over Ni-MOFs. However, to the best of our knowledge, few literature has reported on CuNi-MOFs for AB hydrolysis to date.

In this work, we fabricate the porous CuNi bimetal-organic frameworks with a low-temperature solvothermal strategy. The resulting CuNi-MOFs possess a hierarchical porous structure with high specific surface area and large pore volume. When used as catalysts for the hydrolytic dehydrogenation of AB, CuNi-MOFs exhibit superior catalytic activity and durability, verifying they are promising for the hydrolysis of hydrogen storage materials.

Section snippets

Synthesis of CuNi-MOFs

The porous CuNi-MOFs were prepared with a facile solvothermal method [14]. In brief, copper nitrate trihydrate (Cu(NO₃)₂·3H₂O, 1.85 mg), nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O, 2.2 mg), 4,4′-bipyridine (BPY, 1.56 mg) and polyvinylpyrrolidone (PVP, M_av = 40,000, 10.0 mg) were dissolved into the mixed solution of N,N-dimethylformamide (DMF) and absolute ethanol (V_DMF: V_EtOH = 3: 1, 6.0 mL) in a 10 mL vial. Then, the meso Tetra(4-carboxyphenyl) porphine (TCPP, 98%, 4.0 mg) dissolved in 2 mL of

Results and discussion

Fig. 1 shows the XRD patterns of Cu-MOFs, Ni-MOFs and CuNi-MOFs. Ni-MOFs show a unique tetragonal crystalline phase (JCPDS No. 46–1623). The peaks at 5.3°, 7.5°, 10.5°, 11.9° and 15.0° correspond to the (110), (200), (220), (310) and (400) planes, respectively. Interestingly, the peak of the (110) plane becomes weak when the nickel ions are replaced by Cu²⁺ and it is even indistinguishable in the pattern of Cu-MOFs, which indicates the crystal structure of Cu-MOFs appears to be distorted in

Conclusions

In summary, CuNi bimetal-organic frameworks (CuNi-MOFs) with a hierarchical porous structure are successfully synthesized. When used as catalysts for AB hydrolysis, CuNi-MOFs exhibit excellent catalytic activity and remarkable durability. The corresponding TOF (40.85 mol_H2 · mol_Metal⁻¹ · min⁻¹) and E_a (28.99 kJ mol⁻¹) are competitive, revealing their promising potential for the hydrolytic dehydrogenation of hydrogen storage materials.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This research is supported by the National Natural Science Foundation of China (No. U1304203), the 111 Project (No. B12015) and the Postdoctoral Fellowship Scheme of Hong Kong Polytechnic University (No. #1-YW3F).

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¹: Yong-Ting Li and Sana Ullah contributed equally.

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Short communicationHierarchical porous CuNi-based bimetal-organic frameworks as efficient catalysts for ammonia borane hydrolysis

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Synthesis of CuNi-MOFs

Results and discussion

Conclusions

Declaration of Competing Interest

Acknowledgments

J. Power Sources

Int. J. Hydrog. Energy

Adv. Mater.

J. Catal.

J. Hazard. Mater.

Appl. Catal. A Gen.

Int. J. Hydrog. Energy

Cobalt-ruthenium nanoalloys parceled in porous nitrogen-doped graphene as highly efficient difunctional catalysts for hydrogen evolution reaction and hydrolysis of ammonia borane

ACS Sustain. Chem. Eng.

Highly efficient visible-light-driven catalytic hydrogen evolution from ammonia borane using non-precious metal nanoparticles supported by graphitic carbon nitride

J. Mater. Chem. A

Highly active Ni- and co-based bimetallic catalysts for hydrogen production from ammonia-borane

Front. Chem.

Short communication
Hierarchical porous CuNi-based bimetal-organic frameworks as efficient catalysts for ammonia borane hydrolysis