Shanghai Key Laboratory of Functional Materials Chemistry, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China.
College of Biological, Chemical Science and Engineering, Jiaxing University, Jiaxing 314001, P. R. China.
Acc Chem Res. 2022 May 3;55(9):1301-1312. doi: 10.1021/acs.accounts.2c00097. Epub 2022 Apr 13.
Escalating energy demand, the depletion of fossil fuels, and abnormal climate change are recognized as the key challenges in the 21st century. The valorization of biomass and plastic, representing the most abundant natural and man-made polymers, respectively, as alternatives to fossil fuel is one of the promising solutions to creating a carbon-neutral, waste-free society. Catalysis is an essential tool for manipulating energy transformations via bond-breaking and bond-forming principles. To producing chemicals and fuels via biomass valorization and plastic upcycling, the cleavage of C-O and C-C bonds is the major catalytic route, given that the two are mainly constructed by various interunit C-O and C-C linkages. In this work, a consensus concerning the catalytic mechanism is reached: the activities for the cleavage of C-O and C-C bonds highly depend on the catalyst ability to activate the C-O and C-C bonds. Among the catalysts reported, NbO-based catalysts show a unique, superstrong ability to activate C-O and C-C bonds. While research on biomass valorization over NbO-based catalysts maintains its momentum, plastic upcycling driven by an efficient NbO-based catalyst capable of activating C-O and C-C bonds is quickly catching up. Therefore, deepening the understanding of NbO-based catalysts for the activation of C-O and C-C bonds is of importance to further drive biomass valorization and plastic upcycling, even in many other related areas. Herein, we present progress on the activation of C-O and C-C bonds in waste carbon resources, with an emphasis on our own work in using NbO-based catalysts. First, we introduce NbO-based catalysts for the activation of C-O and C-C bonds in biomass with a special focus on explaining how NbO-based catalysts activate C-O and C-C bonds and why NbO-based catalysts can activate C-O and C-C bonds so efficiently. Then, unified descriptors to embody the abilities to extract O from oxygenated compounds and an adsorbed benzene ring, namely "oxygen affinity" and "benzene ring affinity", were defined to standardize C-O and C-C activation chemistry. Furthermore, we highlight the emerging opportunities of NbO-based catalysts for plastic upcycling by learning the wisdom accumulated from the activation of C-O and C-C bonds in biomass. Finally, our own insights into future recommendations in this promising field are provided.
不断增长的能源需求、化石燃料的枯竭以及异常的气候变化被认为是 21 世纪的关键挑战。将生物质和塑料这两种分别代表最丰富的天然和人造聚合物的物质进行增值利用,是创造碳中和、无废物社会的一种很有前途的解决方案。催化是通过断键和成键原理来操纵能量转化的重要工具。通过生物质增值利用和塑料升级回收来生产化学品和燃料,主要的催化途径是裂解 C-O 和 C-C 键,因为这两者主要由各种单元间的 C-O 和 C-C 键构成。在这项工作中,我们达成了关于催化机制的共识:C-O 和 C-C 键的裂解活性高度依赖于催化剂激活 C-O 和 C-C 键的能力。在所报道的催化剂中,NbO 基催化剂表现出独特的、超强的激活 C-O 和 C-C 键的能力。虽然关于 NbO 基催化剂上的生物质增值利用研究仍在继续,但能够有效激活 C-O 和 C-C 键的高效 NbO 基催化剂驱动的塑料升级回收也在迅速发展。因此,深入了解 NbO 基催化剂对 C-O 和 C-C 键的活化作用对于进一步推动生物质增值利用和塑料升级回收,甚至在许多其他相关领域都具有重要意义。在此,我们介绍了在废碳资源中 C-O 和 C-C 键的活化方面的进展,特别强调了我们在使用 NbO 基催化剂方面的工作。首先,我们介绍了 NbO 基催化剂在生物质中 C-O 和 C-C 键的活化,特别强调解释了 NbO 基催化剂如何激活 C-O 和 C-C 键,以及为什么 NbO 基催化剂能够如此有效地激活 C-O 和 C-C 键。然后,定义了统一的描述符来体现从含氧化合物和吸附的苯环中提取氧的能力,即“氧亲和力”和“苯环亲和力”,以标准化 C-O 和 C-C 键的活化化学。此外,我们通过学习从生物质中 C-O 和 C-C 键的活化中积累的智慧,强调了 NbO 基催化剂在塑料升级回收方面的新兴机遇。最后,我们对这一充满前景的领域提出了自己的未来建议。