Selective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols is a challenging class of reactions, yielding valuable intermediates for the production of pharmaceuticals, perfumes, and flavorings. On monometallic heterogeneous catalysts, the formation of the unsaturated alcohols is thermodynamically disfavored over the saturated aldehydes. Hence, new catalysts are required to achieve the desired selectivity. Herein, the literature of three major research areas in catalysis is integrated as a step toward establishing the guidelines for enhancing the selectivity: reactor studies of complex catalyst materials at operating temperature and pressure, surface science studies of crystalline surfaces in ultrahigh vacuum, and first-principles modeling using density functional theory calculations. Aggregate analysis shows that bimetallic and dilute alloy catalysts significantly enhance the selectivity to the unsaturated alcohols compared to monometallic catalysts. This comprehensive review focuses primarily on the role of different metal surfaces as well as the factors that promote the adsorption of the unsaturated aldehyde via its C═O bond, most notably by electronic modification of the surface and formation of the electrophilic sites. Furthermore, challenges, gaps, and opportunities are identified to advance the rational design of efficient catalysts for this class of reactions, including the need for systematic studies of catalytic processes, theoretical modeling of complex materials, and model studies under ambient pressure and temperature.

中文翻译：

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在双金属和稀合金催化剂上实现高选择性的α，β-不饱和醛加氢的指南：综述

α，β-不饱和醛选择性加氢成不饱和醇是一类具有挑战性的反应，可产生有价值的中间体，用于生产药物，香料和调味剂。在单金属非均相催化剂上，不饱和醇的形成在热力学上优于饱和醛。因此，需要新的催化剂来实现所需的选择性。在此，我们将催化的三个主要研究领域的文献进行整合，以逐步建立提高选择性的指南：在工作温度和压力下对复杂催化剂材料进行反应器研究，在超高真空下对晶体表面进行表面科学研究以及使用密度泛函理论计算的原理建模。聚集分析表明，与单金属催化剂相比，双金属和稀合金催化剂显着提高了对不饱和醇的选择性。这篇全面的综述主要集中在不同金属表面的作用，以及通过不饱和醛的C═O键促进不饱和醛吸附的因素，最主要是通过表面的电子修饰和亲电部位的形成。此外，确定了挑战，差距和机遇，以促进针对此类反应的高效催化剂的合理设计，包括需要对催化过程进行系统研究，对复杂材料进行理论建模以及在环境压力和温度下进行模型研究。