Abstract
Heteroatom-doped Pt-based nanocrystals have generated considerable interest and hold great prospects in heterocatalysis. However, engineering the superficial atomic configurations of these nanocrystals via in situ surface doping remains exceedingly challenging. Herein, we propose a one-pot, in situ surface doping chemical synthesis protocol to prepare quatermetallic PtNiCoRh dendritic nanocrystals as versatile and active catalysts for the electrooxidation of C1 fuels. Leveraging the selective coordination effect between ascorbic acid and Rh3+ ions, the doping of trace Rh atoms can be guided specifically at the near-surface of PtNiCoRh nanocatalysts. Electrocatalytic tests indicate that Pt67Ni16Co16Rh1 nanocrystals with in situ trace Rh-doped surface exhibit substantially enhanced activity, durability, and CO tolerance for the electrooxidation of methanol, formaldehyde, and formic acid. In situ Fourier transform infrared spectroscopy provides molecular-level insight into the exceptional performance of these nanocatalysts. The surface incorporation of anti-corrosive Rh atoms enables the transfer of CO intermediates from the atop Pt sites to the bridged Rh-Pt surface sites, thereby facilitating the elimination of these poisoning species from the catalyst surface. This study presents an effective in situ surface doping strategy which can enable the design of more atom-economic heterocatalysts.
摘要
异质原子掺杂的铂基纳米晶在多相催化领域具有广阔的应用前景, 然而基于原位表面掺杂策略来优化表面原子构型仍颇具挑战. 本研究通过原位表面掺杂的化学方法制备出多枝状PtNi-CoRh四元金属纳米晶. 抗坏血酸和铑离子的配位作用实现了铑离子的延迟还原, 从而可控地将铑原子锚定在催化剂表面层. 电催化研究表明原位表面掺杂的Pt67Ni16Co16Rh1 纳米晶针对甲醇、甲醛和甲酸电氧化都具有优异的催化活性、稳定性及抗CO中毒特性.原位电化学红外光谱结果表明抗腐蚀性强的铑原子的表面掺杂能有效调控催化剂表面Pt位点, 其中CO中毒中间体以更容易氧化消除的桥位态吸附在Rh–Pt异质位点. 本研究提出的原位表面掺杂策略将有助于设计高原子利用率的高效多相催化剂.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (21771067), the Natural Science Foundation of Fujian Province (2017J06005 and 2019J01058), the Program for New Century Excellent Talents in Fujian Province University, the Promotion Program for Young and Middle-aged Teacher in Science and Technology Research of Huaqiao University (ZQN-PY507), and the Scientific Research Funds of Huaqiao University. We also thank the Instrumental Analysis Center of Huaqiao University for the analysis support.
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Xie S and Wang W designed the experiments and analyzed most of the data. Wang W, Chen X, Zhang Y, Han Y, Chen X and Liu K conducted the material synthesis, structural characterizations and catalytic tests. Ye J and Wang W conducted the in situ FTIR tests and analyzed the results. Wang W, Chen X and Xie S wrote the manuscript. All authors contributed to the discussion about the results and the manuscript.
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Wei Wang received his BS degree in chemical engineering from Qingdao University of Science and Technology in 2015, and MS degree in physics from Xiamen University under the supervision of Prof. Shuifen Xie in 2018. From Aug. 2018 to Jul. 2019, he worked as a research assistant at Huaqiao University with Prof. Shuifen Xie. He is currently a PhD candidate at the National University of Singapore. His research interests include the study of inorganic nanocatalysts.
Xuejiao Chen received her BS in 2007 from Southwest University and PhD in physical chemistry in 2013 from Wuhan University. She worked as a postdoctoral fellow in Professor Zhong-Qun Tian’s Group at Xiamen University from 2013 to 2017. She has been an assistant professor at Huaqiao University (Xiamen Campus) since 2017. Her research interests mainly focus on the in situ vibrational spectroscopic study at the electrochemical interfaces.
Shuifen Xie received his BS degree in chemistry (2007) and PhD degree in physical chemistry (2013) from Xiamen University, under the supervision of Prof. Zhaoxiong Xie. From Sep. 2011 to Aug. 2013, he worked as a visiting scholar at Georgia Institute of Technology with Prof. Younan Xia. He is currently a full professor at the College of Materials Science and Engineering, Huaqiao University. His research interests focus on inorganic nanomaterials for catalytic applications and energy storage/conversion.
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Wang, W., Chen, X., Ye, J. et al. In situ surface-doped PtNiCoRh nanocrystals promote electrooxidation of C1 fuels. Sci. China Mater. 64, 1139–1149 (2021). https://doi.org/10.1007/s40843-020-1516-1
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DOI: https://doi.org/10.1007/s40843-020-1516-1