Synthesis methods to prepare lower transition metal catalysts and specifically Ni for Shell‐Isolated Nanoparticle‐Enhanced Raman Spectroscopy (SHINERS) are explored. Impregnation, colloidal deposition, and spark ablation have been investigated as suitable synthesis routes to prepare SHINERS‐active Ni/Au@SiO₂ catalyst/Shell‐Isolated Nanoparticles (SHINs). Ni precursors are confirmed to be notoriously difficult to reduce and the temperatures required are generally harsh enough to destroy SHINs, rendering SHINERS experiments on Ni infeasible using this approach. For colloidally synthesized Ni nanoparticles deposited on Au@SiO₂ SHINs, stabilizing ligands first need to be removed before application is possible in catalysis. The required procedure results in transformation of the metallic Ni core to a fully oxidized metal nanoparticle, again too challenging to reduce at temperatures still compatible with SHINs. Finally, by use of spark ablation we were able to prepare metallic Ni catalysts directly on Au@SiO₂ SHINs deposited on a Si wafer. These Ni/Au@SiO₂ catalyst/SHINs were subsequently successfully probed with several molecules (i. e. CO and acetylene) of interest for heterogeneous catalysis, and we show that they could be used to study the in situ hydrogenation of acetylene. We observe the interaction of acetylene with the Ni surface. This study further illustrates the true potential of SHINERS by opening the door to studying industrially relevant reactions under in situ or operando reaction conditions.

中文翻译：

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镍催化氢化反应的原位壳隔离纳米颗粒增强拉曼光谱。

探索了制备低过渡金属催化剂（特别是用于壳层隔离纳米颗粒增强拉曼光谱（SHINERS）的镍）的合成方法。浸渍、胶体沉积和火花烧蚀已被研究作为制备 SHINERS 活性 Ni/Au@SiO ₂催化剂/壳隔离纳米粒子 (SHINs) 的合适合成路线。众所周知，Ni 前体很难还原，而且所需的温度通常足以破坏 SHIN，这使得使用这种方法对 Ni 进行 SHINERS 实验是不可行的。_{对于沉积在 Au@SiO 2} SHIN上的胶体合成 Ni 纳米粒子，首先需要去除稳定配体，然后才能应用于催化。所需的程序导致金属镍核转变为完全氧化的金属纳米颗粒，这在仍然与 SHIN 兼容的温度下还原也太具有挑战性。最后，通过使用火花烧蚀，我们能够直接在沉积在 Si 晶片上的Au@SiO _{2 SHIN 上制备金属 Ni 催化剂。}随后，这些 Ni/Au@SiO ₂催化剂/SHIN 成功地与多种感兴趣的分子（即CO 和乙炔）进行多相催化探测，我们表明它们可用于研究乙炔的原位加氢。我们观察了乙炔与镍表面的相互作用。这项研究为研究原位或操作反应条件下的工业相关反应打开了大门，进一步说明了 SHINERS 的真正潜力。