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Bacterial cellulose-regulated synthesis of metallic Ni catalysts for high-efficiency electrosynthesis of hydrogen peroxide

细菌纤维素调控合成金属镍催化剂用于高效电合成 过氧化氢

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Abstract

The decentralized production of H2O2via a two-electron oxygen reduction reaction (2e− ORR) has emerged as a promising alternative to the energy-intensive anthraquinone (AQ) process. However, its practical application requires 2e− ORR electrocatalysts with high activity and selectivity. Herein, we report the synthesis of metallic Ni nanoparticles anchored on bacterial cellulose-derived carbon fibers (Ni-NPs/BCCF) via a facile impregnation-pyrolysis method as efficient electrocatalysts for 2e− ORR to H2O2. By tuning the amount of Ni precursor, the best electrocatalytic performance toward 2e− ORR was achieved for Ni-NPs/BCCF-20.7, affording a high H2O2 selectivity of ∼90% and an onset potential of 0.75 V vs. reversible hydrogen electrode (RHE) in an alkaline electrolyte. Ni-NPs/BCCF-20.7 achieved the largest H2O2 yield rate of 162.7 ± 13.7 mmol gcat−1 h−1 and the highest Faradaic efficiency of 93.9% ± 4.2% at 0.2 and 0.5 V vs. RHE from the bulk ORR system, respectively. Theoretical calculations revealed the more favorable “end-on” adsorption configuration of molecular oxygen on the exposed Ni(111) plane, which can effectively suppress the O-O bond dissociation, resulting in high selectivity for H2O2 generation.

摘要

通过两电子氧化还原反应(2e− ORR)原位分散生产过氧化氢 (H2O2)是一种很有前途的、能替代传统的能源密集型蒽醌法的过氧化 氢生产方法. 然而, 其实际应用高度依赖于高活性、高选择性的两电子氧 还原电催化剂的设计与合成, 并且仍面临挑战. 本文利用生物质材料细菌 纤维素调控合成金属镍纳米颗粒, 通过简单的浸渍-热解法得到锚定在细 菌纤维素衍生的碳纤维上的镍纳米颗粒催化剂. 通过调控镍前驱体的用 量, 发现Ni-NPs/BCCF-20.7催化剂具有优异的两电子氧化还原催化性能, 其表现出∼90%的H2O2选择性且起始电位为0.75 V(相对于可逆氢电极 (RHE)). 通过H-Cell恒电位电解, 该催化剂分别在0.2和0.5 V(相对于RHE)得 到最高的H2O2生成速率(162.7±13.7 mmol gcat−1 h−1)和法拉第效率(93.9% ±4.2%). 进一步理论计算表明, 氧气分子在暴露的Ni(111)晶面上具有更 有利的“垂直”吸附构型, 可以有效抑制O–O键的解离, 从而具有较高的 H2O2选择性.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (51872292), China Postdoctoral Science Foundation (E04BFGCV), and the CASHIPS Director’s Fund (YZJJ2021QN18).

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei, 230031, China

    Hui Xu  (徐晖), Meng Jin  (金梦), Jing Geng  (耿竞), Shengbo Zhang  (张圣波) & Haimin Zhang  (张海民)

  2. University of Science and Technology of China, Hefei, 230026, China

    Hui Xu  (徐晖), Meng Jin  (金梦) & Jing Geng  (耿竞)

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  1. Hui Xu  (徐晖)
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  3. Jing Geng  (耿竞)
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  4. Shengbo Zhang  (张圣波)
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Contributions

Xu H conceived the experiments and synthesized the samples; Jin M performed the DFT calculations; Geng J, Zhang S and Zhang H supervised the experiments and gave some suggestions; Xu H wrote the paper with the support from Zhang H. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Shengbo Zhang  (张圣波) or Haimin Zhang  (张海民).

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Conflict of interest

The authors declare that they have no conflict of interest.

Hui Xu obtained his BSc degree from Tianjin University of Technology in 2019. He is currently pursuing his PhD degree under the supervision of Prof. Haimin Zhang at the Institute of Solid State Physics, Chinese Academy of Sciences. His current research interest focuses on the synthesis of metal nanomaterials and their applications in the electrosynthesis of hydrogen peroxide.

Shengbo Zhang obtained his PhD degree from the University of Science and Technology of China in 2020. His current research interest focuses on the synthesis of metal nanomaterials and their applications in electrocatalytic N2 reduction reactions.

Haimin Zhang received his PhD degree from Dalian University of Technology (China) in 2008. He is currently a professor at the Institute of Solid State Physics, Chinese Academy of Sciences. His current research is focused on electrocatalysis and photoelectrocatalysis for energy conversion.

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40843_2021_1795_MOESM1_ESM.pdf

Bacterial cellulose-regulated synthesis of metallic nickel catalysts for high-efficiency electrosynthesis of hydrogen peroxide

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Xu, H., Jin, M., Geng, J. et al. Bacterial cellulose-regulated synthesis of metallic Ni catalysts for high-efficiency electrosynthesis of hydrogen peroxide. Sci. China Mater. 65, 721–731 (2022). https://doi.org/10.1007/s40843-021-1795-9

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