Resisting metal aggregation in pyrolysis of MOFs towards high-density metal nanocatalysts for efficient hydrazine assisted hydrogen production
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Yingwei Li1,3(
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The preparation of supported high-density metal nanoparticles (NPs) is of great importance to boost the performance in heterogeneous catalysis. Thermal transformation of metal-organic frameworks (MOFs) has been demonstrated as a promising route for the synthesis of supported metal NPs with high metal loadings, but it is challenge to achieve uniform metal dispersion. Here we report a strategy of “spatial isolation and dopant anchoring” to resist metal aggregation in the pyrolysis of MOFs through converting a bulk MOF into dual-heteroatom-containing flower-like MOF sheets (B/N-MOF-S). This approach can spatially isolate metal ions and increase the number of anchoring sites, thus efficiently building physical and/or chemical barriers to cooperatively prevent metal NPs from aggregation in the high-temperature transformation process. After thermolysis at 1,000 °C, the B/N-MOF-S affords B,N co-doped carbon-supported Co NPs (Co/BNC) with uniform dispersion and a high Co loading of 37.3 wt.%, while untreated bulk MOFs yield much larger sizes and uneven distribution of Co NPs. The as-obtained Co/BNC exhibits excellent electrocatalytic activities in both hydrogen evolution and hydrazine oxidation reactions, and only a voltage of 0.617 V at a high current density of 100 mA·cm−2 is required when applied to a two-electrode overall hydrazine splitting electrolyzer.
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Resisting metal aggregation in pyrolysis of MOFs towards high-density metal nanocatalysts for efficient hydrazine assisted hydrogen production
), Yingwei Li1,3(
)
Abstract
The preparation of supported high-density metal nanoparticles (NPs) is of great importance to boost the performance in heterogeneous catalysis. Thermal transformation of metal-organic frameworks (MOFs) has been demonstrated as a promising route for the synthesis of supported metal NPs with high metal loadings, but it is challenge to achieve uniform metal dispersion. Here we report a strategy of “spatial isolation and dopant anchoring” to resist metal aggregation in the pyrolysis of MOFs through converting a bulk MOF into dual-heteroatom-containing flower-like MOF sheets (B/N-MOF-S). This approach can spatially isolate metal ions and increase the number of anchoring sites, thus efficiently building physical and/or chemical barriers to cooperatively prevent metal NPs from aggregation in the high-temperature transformation process. After thermolysis at 1,000 °C, the B/N-MOF-S affords B,N co-doped carbon-supported Co NPs (Co/BNC) with uniform dispersion and a high Co loading of 37.3 wt.%, while untreated bulk MOFs yield much larger sizes and uneven distribution of Co NPs. The as-obtained Co/BNC exhibits excellent electrocatalytic activities in both hydrogen evolution and hydrazine oxidation reactions, and only a voltage of 0.617 V at a high current density of 100 mA·cm−2 is required when applied to a two-electrode overall hydrazine splitting electrolyzer.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (Nos. 21825802, 22138003, 22108083, and 52172142), the Foundation of Advanced Catalytic Engineering Research Center of the Ministry of Education (No. 2020AC006), the Science and Technology Program of Qingyuan City (No. 2021YFJH01002), the Natural Science Foundation of Guangdong Province (No. 2017A030312005), the Guangdong University Students Special Fund for Science and Technology Innovation Cultivation (No. pdjh2022a0031), the National Training Program of Innovation and Entrepreneurship for Undergraduates (No. 202210561050), and the Science and Technology Program of Guangzhou (No. 202201010118).
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