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Room-temperature hydrogen spillover achieving stoichiometric hydrogenation of NO3− and NO2− into N2 over CuPd nanowire network

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The development of an efficient hydrogen spillover (HS) catalyst achieves the stoichiometric chemoselective hydrogenation of NO3− and NO2− into N2 at room temperature, which is extremely challenging. Herein, we report a CuxPd1−x nanowire network (NWN) (x = 7, 5, or 3) with tunable hydrogen spillover rate of formic acid (FA) with polyvinylpyrrolidine imine (PVPI) modifying its surface. The presence of PVPI boosts the catalytic selectivity and activity of CuPd NWN for FA dehydrogenation and, more importantly, serves as a modem to tune the HS rate of FA and to stoichiometrically hydrogenate NO3− and NO2− to N2 at room temperature. The density functional theory (DFT) reveals that the CuPd (130 h−1) has a weaker HS rate than AgPd (390 h−1), but the CuPd (> 99%) has a higher utilization of HS than AgPd (31%). Our studies demonstrate a new approach of tuning the FA HS rate and maximizing the application for stoichiometric chemoselective hydrogenation reaction, which will be important for hydrogen generation and its applications.

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摘要

开发一种高效的氢溢出 催化剂, 在室温下实现NO3−和NO2−化学计量选择性加氢为2是极具挑战性的。在此, 我们报道了一种表面由聚乙烯吡咯烷亚胺 (PVPI) 修饰的CuxPd1−x纳米线网络 (NWN) (x = 7, 5或3), 具有可调节的甲酸 (FA) 氢溢出率。PVPI的存在提高了CuPd NWN对甲酸脱氢的催化选择性和活性, 更重要的是, 它可以作为调节甲酸的氢溢出速率的调制解调器, 在室温下将NO3−和NO2−以化学计量方式氢化成N2。密度泛函理论 (DFT)表明, CuPd (130 h−1) 的氢溢出速率低于 AgPd (390 h−1), 但 CuPd (>99%) 的氢溢出利用率高于 AgPd (31%) 。我们的研究展示了一种调节甲酸 氢溢出速率并且最大限度地应用于化学计量化学选择加氢反应, 这对氢气的产生及其应用极为重要。

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Acknowledgements

This work was financially supported by Shaanxi Science Foundation (No. 2021JM-356), the Start-Up Funding for Class D Talent of Xi’an University of Architecture and Technology (No.1608720038), the National Natural Science Foundation of China (Nos. 21871221 and 21602175), the Special Scientific Research Project of Shaanxi Provincial Department of Education (No. 2013JK0874) and the Key Research and Development Program in Shaanxi Province (No. 2019SF-241).

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Author notes

  1. Ruo-Yan Miao and Xue-Xiang Li have contributed equally to this work.

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Xi’an University of Architecture and Technology, Xi’an, 710055, China

    Ruo-Yan Miao, Qian Lei, Hu Liu, Zuo-Bin Tang, Liang Zhang & Yu-Hong Tian

  2. Department of Physics, Beijing Technology and Business University, Beijing, 100048, China

    Zhen-Hui Ma & Xu-Dong Liu

  3. School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an, 710072, China

    Xue-Xiang Li

  4. Department of Chemistry, University of Virginia, Charlottesville, VA, 22904, USA

    Zhou-Yang Yin

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  1. Ruo-Yan Miao
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Miao, RY., Li, XX., Lei, Q. et al. Room-temperature hydrogen spillover achieving stoichiometric hydrogenation of NO3− and NO2− into N2 over CuPd nanowire network. Rare Met. 41, 851–858 (2022). https://doi.org/10.1007/s12598-021-01854-6

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