Diverse N-doped carbon-supported non-noble metal nanostructures (Ni, Co, Fe, Cu) are designed, and explored in selective butadiene hydrogenation. Focusing on particle size and composition, optimal catalytic performance is observed with Ni catalysts, where smaller metallic Ni particles of ca. 6.2 nm exhibit superior activity and larger ones (14–47 nm) display much higher total butene selectivity. An integral approach combining detailed kinetics, chemisorption, and dual-beam Fourier transform infrared spectroscopic study is performed to rationalize the Ni particle size effect. The findings reveal that smaller Ni particles offer improved activation of butadiene and hydrogen due to advantageous adsorption dynamics. Spectroscopic examinations further suggest different adsorption configurations existing on Ni particles, with larger particles displaying strong π-adsorption, which impedes hydrogen replacement. Additionally, the stability of the catalysts is scrutinized under various reaction conditions, revealing that deactivation occurs more rapidly at lower temperatures, primarily due to mild coke deposition.

中文翻译：

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N 掺杂碳承载的非贵金属纳米结构上的丁二烯加氢


设计了多种 N 掺杂碳负载的非贵金属纳米结构 （Ni， Co， Fe， Cu），并在选择性丁二烯加氢中进行了探索。专注于粒度和组成，使用 Ni 催化剂观察到最佳催化性能，其中约 6.2 nm 的较小金属 Ni 颗粒表现出优异的活性，而较大的金属 Ni 颗粒 （14–47 nm） 表现出更高的总丁烯选择性。采用一种结合详细动力学、化学吸附和双光束傅里叶变换红外光谱研究的积分方法，使 Ni 粒度效应合理化。研究结果表明，由于有利的吸附动力学，较小的 Ni 颗粒提供了更好的丁二烯和氢的活化。光谱检查进一步表明 Ni 颗粒上存在不同的吸附配置，较大的颗粒表现出强烈的π吸附，这阻碍了氢的置换。此外，在各种反应条件下对催化剂的稳定性进行仔细检查，结果表明，在较低温度下，失活发生得更快，这主要是由于轻微的焦炭沉积。