Nanoporous Ni3P Evolutionarily Structured onto a Ni Foam for Highly Selective Hydrogenation of Dimethyl Oxalate to Methyl Glycolate
Nanoporous Ni3P Evolutionarily Structured onto a Ni Foam for Highly Selective Hydrogenation of Dimethyl Oxalate to Methyl Glycolate
复制标题
纳米多孔 Ni3P 进化结构在镍泡沫上，用于草酸二甲酯高选择性氢化为乙醇酸甲酯
DOI：
10.1021/acsami.9b11703
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发表时间：
2019
影响因子：
9.5
通讯作者：
Lu Yong
中科院分区：
文献类型：
--
作者：
Zhu Jian;Cao Liqun;Li Cuiyu;Zhao Guofeng;Zhu Tong;Hu Wei;Sun Weidong;Lu Yong
乙醇酸甲酯（MG）是一种多功能平台分子，可用于生产许多重要的化学品和材料，特别是新一代生物相容性和可生物降解的聚乙醇酸。原则上，它可以通过CO衍生的草酸二甲酯（DMO）的气相加氢从合成气（CO + H2）中大规模生产，但突破性的催化剂代表了一个巨大的挑战。在这里，我们报告了Ni泡沫结构的纳米多孔Ni 3 P催化剂的发现，该催化剂由从纳米尺度到宏观尺度设计的Ni 2 P/Ni泡沫演变而来，能够以>95%的选择性几乎完全将DMO转化为MG，并且稳定至少1000小时而没有任何失活的迹象。动力学实验和理论计算表明，与Ni 2 P相比，Ni 3 P具有更高的表面电子密度，有利于MG以分子方式而非解离方式吸附，并具有更高的MG加氢生成乙二醇（EG）的活化能，从而显著抑制MG过度加氢生成EG。
Methyl glycolate (MG) is a versatile platform molecule to produce numerous important chemicals and materials, especially new-generation biocompatible and biodegradable poly(glycolic acid). In principle, it can be massively produced from syngas (CO + H2) via gas-phase hydrogenation of CO-derived dimethyl oxalate (DMO), but the groundbreaking catalyst represents a grand challenge. Here, we report the discovery of a Ni-foam-structured nanoporous Ni3P catalyst, evolutionarily transformed from a Ni2P/Ni-foam engineered from nano- to macro-scale, being capable of nearly fully converting DMO into MG at >95% selectivity and stable for at least 1000 h without any sign of deactivation. As revealed by kinetic experiments and theoretical calculations, in comparison with Ni2P, Ni3P achieves a higher surface electron density that is favorable for MG adsorption in a molecular manner rather than in a dissociative manner and has much higher activation energy for MG hydrogenation to ethylene glycol (EG), thereby markedly suppressing its overhydrogenation to EG.