Controlled Surface Modification of Cobalt Phosphide with Sulfur Tunes Hydrogenation Catalysis,Journal of the American Chemical Society

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Controlled Surface Modification of Cobalt Phosphide with Sulfur Tunes Hydrogenation Catalysis
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-10-24 , DOI: 10.1021/jacs.3c07312
Nina A Arnosti ₁ , Vanessa Wyss ₁ , Murielle F Delley ₁

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Transition metal phosphides have shown promise as catalysts for water splitting and hydrotreating, especially when a small amount of sulfur is incorporated into the phosphides. However, the effect of sulfur on catalysis is not well understood. In part, this is because conventional preparation methods of sulfur-doped transition metal phosphides lead to sulfur both inside and at the surface of the material. Here, we present an alternative method of modifying cobalt phosphide (CoP) with sulfur using molecular S-transfer reagents, namely, phosphine sulfides (SPR₃). SPR₃ added sulfur to the surface of CoP and using a series of SPR₃ reagents having different P═S bond strengths enabled control over the amount and type of sulfur transferred. Our results show that there is a distribution of different sulfur sites possible on the CoP surface with S-binding strengths in the range of 69 to 84 kcal/mol. This provides fundamental information on how sulfur binds to an amorphous CoP surface and provides a basis to assess how number and type of sulfur on CoP influences catalysis. For the catalytic hydrogenation of cinnamaldehyde, intermediate amounts of sulfur with intermediate binding strengths at the surface of CoP were optimal. With some but not too much sulfur, CoP exhibited a higher hydrogenation productivity and a decreased formation of secondary reaction products. Our work provides important insight into the S-effect on the catalysis by transition metal phosphides and opens new avenues for catalyst design.

中文翻译：

硫调加氢催化磷化钴的受控表面改性

过渡金属磷化物已显示出作为水分解和加氢处理催化剂的前景，特别是当磷化物中掺入少量硫时。然而，硫对催化的影响尚不清楚。部分原因是硫掺杂过渡金属磷化物的常规制备方法会导致材料内部和表面产生硫。在这里，我们提出了另一种使用分子 S 转移试剂（即硫化膦(SPR ₃ ) ）用硫修饰磷化钴 ( CoP ) 的方法。SPR _{3将硫添加到}CoP表面，并使用一系列具有不同 P=S 键强度的 SPR ₃试剂，可以控制转移的硫的量和类型。我们的结果表明， CoP表面上可能分布着不同的硫位点，硫结合强度在 69 至 84 kcal/mol 范围内。这提供了有关硫如何与无定形CoP表面结合的基本信息，并为评估CoP上硫的数量和类型如何影响催化提供了基础。对于肉桂醛的催化氢化， CoP表面具有中等结合强度的中等量的硫是最佳的。使用一些但不是太多的硫时，CoP表现出更高的加氢生产率并减少副反应产物的形成。我们的工作为过渡金属磷化物催化的 S 效应提供了重要的见解，并为催化剂设计开辟了新的途径。

更新日期：2023-10-24

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