Interfacial charge effects of supported-metal-cluster heterostructures on azo hydrogenation catalyzation
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The impact of interfacial charge on catalytic performance of supported-metal-cluster (SMC) heterostructures remains unclear, hindering efforts to develop high-performance SMC catalysts. Herein we systematically investigated interfacial charge effects of SMCs using a model system of graphene-supported gold-nanoclusters (AuNCs/rGO) for azo hydrogenation. Three types of SMCs with different interfacial charges were synthesized by anchoring electropositive 2-aminoethanethiol (CSH), amphoteric cysteine (Cys), and electronegative 3-mercaptopropionic-acid (MPA) onto AuNCs/rGO, respectively. All three SMCs exhibited high and selective catalytic activity to azo-hydrogenation in four representative azo dyes. The catalytic activity of Cys@AuNCs/rGO was lower than that of CSH@AuNCs/rGO but higher than that of MPA@AuNCs/rGO. However, the cyclic stability of Cys@AuNCs/rGO was inferior to that of both CSH@AuNCs/rGO and MPA@AuNCs/rGO. Further mechanistic studies revealed that amino ligands modified CSH@AuNCs and Cys@AuNCs agglomerated into large-size gold nanoparticles on rGO surface during catalytic reaction under NaBH4 action, leading to reduced efficiency and cyclic stability. Conversely, non-amino ligand modified MPA@AuNCs only partially detached from rGO surface without agglomeration, resulting in better cyclic stability. Protection of amino groups in ligands such as modifying –NH3+ group in Cys into imine to form N-isobutyryl-L-cysteine (NIBC) substantially improved the cyclic stability while maintaining the high activity in the NIBC@AuNCs/rGO catalyst system. Our work provides an approach for developing a highly-active and stable SMC heterostructure catalyst via manipulating interfacial charges in SMC.
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Interfacial charge effects of supported-metal-cluster heterostructures on azo hydrogenation catalyzation
Abstract
The impact of interfacial charge on catalytic performance of supported-metal-cluster (SMC) heterostructures remains unclear, hindering efforts to develop high-performance SMC catalysts. Herein we systematically investigated interfacial charge effects of SMCs using a model system of graphene-supported gold-nanoclusters (AuNCs/rGO) for azo hydrogenation. Three types of SMCs with different interfacial charges were synthesized by anchoring electropositive 2-aminoethanethiol (CSH), amphoteric cysteine (Cys), and electronegative 3-mercaptopropionic-acid (MPA) onto AuNCs/rGO, respectively. All three SMCs exhibited high and selective catalytic activity to azo-hydrogenation in four representative azo dyes. The catalytic activity of Cys@AuNCs/rGO was lower than that of CSH@AuNCs/rGO but higher than that of MPA@AuNCs/rGO. However, the cyclic stability of Cys@AuNCs/rGO was inferior to that of both CSH@AuNCs/rGO and MPA@AuNCs/rGO. Further mechanistic studies revealed that amino ligands modified CSH@AuNCs and Cys@AuNCs agglomerated into large-size gold nanoparticles on rGO surface during catalytic reaction under NaBH4 action, leading to reduced efficiency and cyclic stability. Conversely, non-amino ligand modified MPA@AuNCs only partially detached from rGO surface without agglomeration, resulting in better cyclic stability. Protection of amino groups in ligands such as modifying –NH3+ group in Cys into imine to form N-isobutyryl-L-cysteine (NIBC) substantially improved the cyclic stability while maintaining the high activity in the NIBC@AuNCs/rGO catalyst system. Our work provides an approach for developing a highly-active and stable SMC heterostructure catalyst via manipulating interfacial charges in SMC.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (Nos. 52273110, 21975191, 52372271 and 22173070), the Knowledge Innovation Program of Wuhan Shuguang Project, and the Fundamental Research Funds for the Central Universities (WUT: 2023III013GX).
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