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Modification of Nickel Surfaces by Bismuth: Effect on Electrochemical Activity and Selectivity toward Glycerol
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2020-03-19 , DOI: 10.1021/acsami.9b22378
Mohamed S. E. Houache 1 , Kara Hughes 1 , Reza Safari 2 , Gianluigi A. Botton 2 , Elena A. Baranova 1
Affiliation  

Herein, we study the effect of adding bismuth to Ni-nanostructured catalysts (NixBi1–x, x = 100–90 at. %) for glycerol electro-oxidation in alkaline solution by combining physiochemical, electrochemical, and in situ infrared spectroscopy techniques, as well as continuous electrolysis with HPLC (high-performance liquid chromatography) product analysis. The addition of small quantities of Bi (<20 at. %) to Ni nanoparticles led to significant activity enhancement at lower overpotentials, with Ni90Bi10 displaying an over 2-fold increase compared to Ni. Small quantities of bismuth actively affected the reaction selectivity of Ni by suppressing the pathways with C–C bond cleavage, hindering the production of carbonate and formate and improving the formation of tartronate, oxalate, and glycerate. Furthermore, the effect of aging on NixBi1–x catalysts was investigated, resulting in structural modification from the Ni–Bi double shell/core structure to Bi decorated on the folded Ni sheet, thus enhancing their activity twice after 2 weeks of aging. NiBi catalysts are promising candidates for glycerol valorization to high-value-added products.

中文翻译:

铋对镍表面的改性:对电化学活性和对甘油选择性的影响

在这里,我们通过结合物理化学,电化学和原位红外光谱研究了在碱溶液中的甘油电氧化过程中,将铋添加到镍纳米结构催化剂(Ni x Bi 1– xx = 100–90 at。%)中的效果。技术,以及用HPLC(高效液相色谱)产品分析进行连续电解。在Ni纳米粒子中添加少量Bi(<20 at。%)可以在较低的超电势下显着增强活性,其中Ni 90 Bi 10与Ni相比,显示出超过2倍的增长。少量的铋通过抑制C–C键断裂的途径,抑制碳酸盐和甲酸盐的产生并改善酒石酸盐,草酸盐和甘油酸盐的形成,从而积极地影响Ni的反应选择性。此外,研究了时效对Ni x Bi 1- x催化剂的影响,导致了结构的改变,从Ni-Bi双壳/核结构变为折叠后的Ni片上装饰的Bi,从而在老化2周后两次提高了它们的活性。 。NiBi催化剂有望成为甘油增值到高附加值产品的候选材料。
更新日期:2020-03-20
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