Owing to the high economic values and broad applications of diols with various alkyl chains, the development of efficient heterogeneous catalysts for the highly chemoselective synthesis of diols is highly desirable. In this work, a range of bifunctional Cu_x/Mg_3-xAlO (x = 0.5, 1, 1.5, 2) nanocatalysts derived from layered double hydroxides (LDHs) precursors were fabricated and evaluated in the selective hydrogenation of lactones to synthesize diols. Systematic structure characterizations indicated the bifunctional catalytic sites containing active Cu nanoparticles with controllable sizes and tunable base sites could be finely constructed in the Cu_x/Mg_3-xAlO catalysts. Intrinsic catalytic activity tests were conducted to reveal the structure-activity relationship in the model reaction of selective hydrogenation of γ-valerolactone (GVL) to produce 1,4-pentanediol (1,4-PeD); it was found that the optimal bifunctional Cu_1.5/Mg_1.5AlO catalyst exhibited greatly improved catalytic activity and selectivity for this reaction, which surpassed various copper-based reference catalysts; the excellent catalytic performance of Cu_1.5/Mg_1.5AlO was mainly attributed to the cooperative effect of the well-dispersed active Cu nanoparticles and the appropriate surface base sites nearby. Moreover, the bifunctional Cu_1.5/Mg_1.5AlO catalyst could be extended to other lactones with different ring sizes. This work provides a low-cost, environmentally benign and atom-economic heterogeneous catalytic system for the highly selective and sustainable synthesis of value-added diols.

由于具有各种烷基链的二醇的高经济价值和广泛应用，迫切需要开发用于二醇的高化学选择性合成的有效多相催化剂。在这项工作中，制备了一系列从层状双氢氧化物（LDHs）前体衍生的双功能Cu _x / Mg _3-x AlO（x = 0.5、1、1.5、2）纳米催化剂，并在内酯的选择性加氢合成二醇中进行了评估。 。系统结构表征表明，可以在Cu _x / Mg _3-x中精细构建双功能催化位点，该位点包含具有可控制大小和可调碱位的活性Cu纳米粒子AlO催化剂。进行了内在催化活性测试，揭示了在选择性氢化γ-戊内酯（GVL）生成1,4-戊二醇（1,4-PeD）的模型反应中的构效关系。结果发现，最佳的双功能Cu _1.5 / Mg _1.5 AlO催化剂表现出大大提高的催化活性和选择性，超过了各种铜基参比催化剂。Cu _1.5 / Mg _1.5 AlO的优异催化性能主要归因于活性Cu纳米颗粒分散良好以及附近合适的表面碱位的协同作用。另外，双功能Cu _1.5 / Mg _1.5AlO催化剂可以扩展到具有不同环尺寸的其他内酯。这项工作为增值二醇的高度选择性和可持续合成提供了一种低成本，对环境无害且原子经济的多相催化体系。