Highly selective electrosynthesis of 3,4-dihydroisoquinoline accompanied with hydrogen production over three-dimensional hollow CoNi-based microarray electrocatalysts
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Electrocatalytic oxidation reaction of biomass-based derivatives is an excellent candidate to replace water oxidation for obtaining both value-added products and hydrogen (H2), but the exploration of competent electrocatalysts is still highly challenging. Herein, two new types of three-dimensional self-supported hollow microarrays containing CoNi layered double hydroxide (CoNi-LDH) and N-doped carbon nanosheets decorated with CoNi alloyed nanoparticles (CoNi-NC) on carbon cloth (CC) are prepared, which are further used as efficient electrocatalysts for tetrahydroisoquinoline (THIQ) electrooxidation and hydrogen evolution reaction (HER), respectively. We demonstrate that the Co-modulated electronic environment for Ni(II)/Ni(III) redox-looping in CoNi-LDH is the main factor to boost the selectivity of 3,4-dihydroisoquinoline (DHIQ) for the indirect electrooxidation process of THIQ. Density functional theory (DFT) calculations reveal that the Ni(III)/Co(III) dual sites of CoNi-LDH exhibit enhanced adsorption for THIQ but poorer adsorption for DHIQ compared to pure Co(III) or Ni(III). Therefore, the Ni(III)/Co(III) dual sites can effectively inhibit the peroxidation of DHIQ to isoquinoline (IQ) over CoNi-LDH, thus improving the selectivity of DHIQ to nearly 100%, much higher than that of its pure Ni counterpart. Moreover, CC@CoNi-NC can deliver high HER activity with low overpotential (40 mV@10 mA·cm−2) and high exchange current density (3.08 mA·cm−2). Impressively, the assembled flow-cell device with CC@CoNi-LDH anode and CC@CoNi-NC cathode only requires low cell voltage and electricity consumption of 1.6 V and 3.50 kWh per cubic meter of H2 (@25 mA·cm−2).
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Highly selective electrosynthesis of 3,4-dihydroisoquinoline accompanied with hydrogen production over three-dimensional hollow CoNi-based microarray electrocatalysts
)
Abstract
Electrocatalytic oxidation reaction of biomass-based derivatives is an excellent candidate to replace water oxidation for obtaining both value-added products and hydrogen (H2), but the exploration of competent electrocatalysts is still highly challenging. Herein, two new types of three-dimensional self-supported hollow microarrays containing CoNi layered double hydroxide (CoNi-LDH) and N-doped carbon nanosheets decorated with CoNi alloyed nanoparticles (CoNi-NC) on carbon cloth (CC) are prepared, which are further used as efficient electrocatalysts for tetrahydroisoquinoline (THIQ) electrooxidation and hydrogen evolution reaction (HER), respectively. We demonstrate that the Co-modulated electronic environment for Ni(II)/Ni(III) redox-looping in CoNi-LDH is the main factor to boost the selectivity of 3,4-dihydroisoquinoline (DHIQ) for the indirect electrooxidation process of THIQ. Density functional theory (DFT) calculations reveal that the Ni(III)/Co(III) dual sites of CoNi-LDH exhibit enhanced adsorption for THIQ but poorer adsorption for DHIQ compared to pure Co(III) or Ni(III). Therefore, the Ni(III)/Co(III) dual sites can effectively inhibit the peroxidation of DHIQ to isoquinoline (IQ) over CoNi-LDH, thus improving the selectivity of DHIQ to nearly 100%, much higher than that of its pure Ni counterpart. Moreover, CC@CoNi-NC can deliver high HER activity with low overpotential (40 mV@10 mA·cm−2) and high exchange current density (3.08 mA·cm−2). Impressively, the assembled flow-cell device with CC@CoNi-LDH anode and CC@CoNi-NC cathode only requires low cell voltage and electricity consumption of 1.6 V and 3.50 kWh per cubic meter of H2 (@25 mA·cm−2).
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Acknowledgements
We gratefully acknowledge the financial support from the Natural Science Foundation of Guangdong Province (No. 2023B1515040005), the National Natural Science Foundation of China (Nos. 22378135, 21825802, and 22138003), and the State Key Laboratory of Pulp and Paper Engineering (No. 2022PY05). The authors acknowledged the HPC resources provided from the University of Stavanger. The authors would like to thank Mr. Jiawei Jiang from Shiyanjia Lab (www.shiyanjia.com) for the XPS analysis.
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