通过选择性 Caryl-O(C)键裂解实现木质素 β-O-4 连接的水电催化加氢解聚:吸附的调节。

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Journal of the American Chemical Society Pub Date : 2024-11-05 DOI:10.1021/jacs.4c12220
Yuanqing He, Xu Zeng, Zhuoran Lu, Shiheng Mo, Qizheng An, Qinghua Liu, Yulu Yang, Wu Lan, Shuangyin Wang, Yuqin Zou
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引用次数: 0

摘要

木质素 β-O-4 键的苯氧键(Caryl-O(C))的裂解有望缓解降解产物的缩合,提高产品价值。然而,由于高解离能(∼409 kJ mol-1)和芳香族化合物容易过度还原,目前尚未实现电化学断裂 Caryl-O(C)键。在此,我们报告了一种通过调节分子吸附来断开 Caryl-O(C)键的水电化学还原策略。密度泛函理论(DFT)计算和石英晶体微天平(QCM)测量结果表明,CuO 电催化剂中残留的 Cu(I) 可增强 2-苯氧基-1-苯乙醇(PPE)对 Caryl-O(C)键的吸附,并降低质子攻击 β-O-4 连接中氧原子的能垒。因此,与铜电催化剂(对苯二酚的产率为 47.4%,苯甲醇的产率为 24.8%)相比,CuO 纳米棒在电位为 -0.4 V 的不分化电池中与可逆氢电极(RHE)相比,表现出更高的对苯二酚产率(95.3%)和苯甲醇产率(88.6%)。此外,通过结合原位同步辐射傅立叶变换红外光谱(SR-FTIR)和 DFT 计算,确定了反应途径和 Caryl-O(C)键的裂解。这种有效的方法被用于杨木木质素电解,产生了 10.9 重量百分比的愈创木酰基甘油,选择性大于 63.0%。这项研究提供了一种高效、温和的方法,用于裂解木质素中的 Caryl-O(C)键。
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Aqueous Electrocatalytic Hydrogenation Depolymerization of Lignin β-O-4 Linkage via Selective Caryl-O(C) Bond Cleavage: The Regulation of Adsorption.

The cleavage of the benzene-oxygen (Caryl-O(C)) bond of the lignin β-O-4 linkage is expected to relieve condensation of the degradation product and improve the product value. Nevertheless, the electrochemical breaking of the Caryl-O(C) bond has not been achieved yet due to the high dissociation energy (∼409 kJ mol-1) and the easy over-reduction of aromatic compounds. Here, we report an aqueous electrochemical reduction strategy for breaking Caryl-O(C) bonds via the regulation of molecular adsorption. The density functional theory (DFT) calculations and quartz crystal microbalance (QCM) measurements reveal that the residual Cu(I) in the CuO electrocatalyst enhances the adsorption of the 2-phenoxy-1-phenylethyl alcohol (PPE) by the Caryl-O(C) bond and lowers the energy barrier of the protons attacking the oxygen atom in the β-O-4 linkage. Thus, compared to the Cu electrocatalyst (with a hydroquinone yield of 47.4% and a benzyl alcohol yield of 24.8%), the CuO nanorod exhibits a much higher yield of hydroquinone (95.3%) and benzyl alcohol (88.6%) at a potential of -0.4 V vs reversible hydrogen electrode (RHE) in an undivided cell. Moreover, the reaction pathway and the cleavage of the Caryl-O(C) bond are identified through a combination of in situ synchrotron-radiation Fourier transformed infrared spectroscopy (SR-FTIR) and DFT calculations. This effective method is utilized for poplar lignin electrolysis, yielding 10.9 wt % of guaiacylglycerol, with an outstanding selectivity of >63.0%. This work provides an efficient and mild method of cleavage of Caryl-O(C) bonds in lignin valorization.

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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
期刊最新文献
Aqueous Electrocatalytic Hydrogenation Depolymerization of Lignin β-O-4 Linkage via Selective Caryl-O(C) Bond Cleavage: The Regulation of Adsorption. Activating the Mn Single Atomic Center for an Efficient Actual Active Site of the Oxygen Reduction Reaction by Spin-State Regulation. Site-Specific Histidine Aza-Michael Addition in Proteins Enabled by a Ferritin-Based Metalloenzyme Impurities in Arylboronic Esters Induce Persistent Afterglow Antiaromatic Metallacyclopentatriene Complexes.
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