Chen Pengjing, Zhao Guofeng, Shi Xue-Rong, Zhu Jian, Ding Jia, Lu Yong
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, East China Normal University, Shanghai 200062, China.
School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China.
iScience. 2019 Jul 26;17:315-324. doi: 10.1016/j.isci.2019.07.006. Epub 2019 Jul 5.
CO circular economy is urgently calling for the effective large-scale CO reutilization technologies. The reverse water-gas shift (RWGS) reaction is the most techno-economically viable candidate for dealing with massive-volume CO via downstream mature Fischer-Tropsch and methanol syntheses, but the desired groundbreaking catalyst represents a grand challenge. Here, we report the discovery of a nano-intermetallic InNiC catalyst, for example, being particularly active, selective, and stable for the RWGS reaction. The InNiC(111) surface is dominantly exposed and gifted with dual active sites (3Ni-In and 3Ni-C), which in synergy efficiently dissociate CO into CO* (on 3Ni-C) and O* (on 3Ni-In). O* can facilely react with 3Ni-C-offered H* to form HO. Interestingly, CO* is mainly desorbed at and above 400°C, whereas alternatively hydrogenated to CHOH highly selectively below 300°C. Moreover, this nano-intermetallic can also fully hydrogenate CO-derived dimethyl oxalate to ethylene glycol (commodity chemical) with high selectivity (above 96%) and favorable stability.
二氧化碳循环经济迫切需要有效的大规模二氧化碳再利用技术。逆水煤气变换（RWGS）反应是通过下游成熟的费托合成和甲醇合成来处理大量二氧化碳的最具技术经济可行性的选择，但所需的突破性催化剂是一个巨大的挑战。在此，我们报告发现了一种纳米金属间化合物InNiC催化剂，例如，它对RWGS反应具有特别高的活性、选择性和稳定性。InNiC(111)表面占主导地位，具有双活性位点（3Ni-In和3Ni-C），它们协同作用可有效地将二氧化碳分解为CO*（在3Ni-C上）和O*（在3Ni-In上）。O可以很容易地与3Ni-C提供的H反应形成HO。有趣的是，CO*主要在400°C及以上脱附，而在300°C以下则高度选择性地氢化为CHOH。此外，这种纳米金属间化合物还可以将由二氧化碳衍生的草酸二甲酯完全氢化为乙二醇（商品化学品），具有高选择性（高于96%）和良好的稳定性。
