Mechanism of Asymmetric “Ru–B” Double Site Synergy in Breaking C–C Bonds of Lignin Derivatives in Bio-char

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2024-10-03 DOI:10.1021/acscatal.4c0449110.1021/acscatal.4c04491

Zhiyuan Tang, Qi Zhang*, Yishuang Wang*, Yuzhen Hu, Longlong Ma, Mingqiang Chen, Xinghua Zhang and Lungang Chen,

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引用次数: 0

Abstract

The ring opening of an aromatic ring is the key step of lignin depolymerization (LD) to obtain high-value-added fatty alcohol compounds. Bio-char catalysts with nonmetallic boron (B) and d-p hybrid of C-Ru sites were prepared by an amino-assisted coordination strategy, and used for lignin derivatives conversion in supercritical ethanol systems. Metal-nonmetal interface sites composed of Ru clusters and Csp³-N-BO₃ exhibited the optimal orbital energy level and active electronic state. In Ru and B interface sites, the attraction of Ru empty d orbitals to π electron clouds of the benzene ring, along with electron exchange between B anti-bonding orbitals and hydroxyl oxygen of the benzene ring side chain, was synergically coupled. This coupling led to a reduction in the stability of π electron clouds within the benzene ring and easy opening, ultimately achieving a conversion rate of 99.2% for lignin derivatives. During the adsorption process, d-band centers of Ru and enhanced localization of B-site electronic states led to a certain directionality of the benzene ring transformation, thereby effectively enhancing the catalytic selectivity toward 1-hexanol, with a yield of 29.7%. This study elucidates the criteria for designing efficient LD catalysts by synergistically utilizing metal d orbitals and non-metal antibonding orbitals.

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不对称 "Ru-B "双位点协同作用在生物炭中破坏木质素衍生物 C-C 键的机理

芳香环的开环是木质素解聚（LD）获得高附加值脂肪醇化合物的关键步骤。通过氨基辅助配位策略制备了具有非金属硼（B）和 C-Ru d-p 杂化位点的生物炭催化剂，并将其用于超临界乙醇体系中的木质素衍生物转化。由 Ru 簇和 Csp3-N-BO3 组成的金属-非金属界面位点表现出最佳的轨道能级和活性电子态。在 Ru 和 B 的界面位点中，Ru 空 d 轨道对苯环的 π 电子云的吸引，以及 B 反键轨道和苯环侧链羟基氧之间的电子交换是协同耦合的。这种耦合作用降低了苯环内 π 电子云的稳定性，使其易于打开，最终使木质素衍生物的转化率达到 99.2%。在吸附过程中，Ru 的 d 带中心和 B 位电子态的局域化增强导致苯环转化具有一定的方向性，从而有效提高了对 1- 己醇的催化选择性，产率达到 29.7%。这项研究阐明了通过协同利用金属 d 轨道和非金属反键轨道设计高效 LD 催化剂的标准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.