Ring-opening of furfuryl alcohol to pentanediol with hierarchically structured Cu-MFI catalysts
Ring-opening of furfuryl alcohol to pentanediol with hierarchically structured Cu-MFI catalysts
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DOI：
10.1016/j.micromeso.2023.112484
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发表时间：
2023-02
影响因子：
5.2
通讯作者：
Dengfeng Dai;Yu Shi;Feng Chao;Dandan Liu;L. Yunqi
中科院分区：
文献类型：
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作者：
Dengfeng Dai;Yu Shi;Feng Chao;Dandan Liu;L. Yunqi
金属-酸双功能催化剂经常遇到由于积碳和金属团聚而导致的失活问题。在此，开发了一种分级多孔结构的 Cu-MFI-AEH 催化剂，用于糠醇选择性开环生成戊二醇，其戊二醇收率 >90% 并提高了稳定性。纳米铜物质和布朗斯台德酸质子的协同作用促进了糠醇的开环。 DFT技术也揭示了小尺寸Cu具有更好的氢离解性能，并且≡Si(OH)Al≡(Brønsted酸性质子)的引入促进了糠醇的吸附，降低了糠醇的开环能垒。所得高孔催化剂具有较大的外表面积和较大的孔体积，有利于提供可及的活性位点并加速产物传输，最终产生优异的抗结焦性能。此外，经氨处理产生的MFI表面丰富的硅烷醇基团可以作为接枝Cu物种的锚定位点，从而产生强的金属-载体相互作用和高抗烧结性能。本文报道的结果提供了一种提高铜基催化剂稳定性和活性的新策略。它还激发了生物质资源转化为高附加值含氧精细化学品。
Metal-acid bifunctional catalysts often encounter deactivation troubles due to carbon deposition and metal agglomeration. Herein, a hierarchically porous structured Cu-MFI-AEH catalyst was developed for selective ring-opening of furfuryl alcohol to pentanediols, which exhibits >90% yield of pentanediols and improved stability. The synergistic effect of nano-copper species and Brønsted acidic protons boosts the ring opening of furfuryl alcohol. This was also disclosed by the DFT technique that small-size Cu possesses better hydrogen dissociation performance, and the introduction of ≡Si (OH) Al≡ (Brønsted acidic protons) promotes the adsorption of furfuryl alcohol and reduces the ring opening energy barrier of furfuryl alcohol. The obtained highly porous catalyst possesses a large external surface area and large pore volume, which are beneficial to offer accessible active sites and accelerate product transport, eventually resulting in superior anti-coking performance. Furthermore, the abundant silanol groups on the MFI surface produced by ammonia treatment could act as an anchoring site for grafting Cu species, resulting in strong metal-support interaction and highly anti-sintering performance. The results reported herein provide a novel strategy to improve the stability and activity of copper-based catalysts. It also inspires the conversion of biomass resources into high value-added oxygenated fine chemicals.