Cu催化羟基自由基氧化断裂纤维二糖分子糖苷键反应及其在纤维素低温解聚中的应用

doi:10.1016/S1872-2067(20)63569-0

催化学报 ›› 2020, Vol. 41 ›› Issue (7): 1073-1080.DOI: 10.1016/S1872-2067(20)63569-0

Cu催化羟基自由基氧化断裂纤维二糖分子糖苷键反应及其在纤维素低温解聚中的应用

顾方伟, 刘海超

北京大学化学与分子工程学院, 北京分子科学国家研究中心, 北京 100871

收稿日期:2019-12-08 出版日期:2020-07-18 发布日期:2020-04-18
通讯作者: 刘海超
基金资助:
国家重点基础研究发展计划（2016YFB0701100）；国家自然科学基金（21690081，21433001，21832001，21821004）；北京分子科学国家实验室基金（BNLMS-CXXM-201905）.

Hydroxyl radicals-mediated oxidative cleavage of the glycosidic bond in cellobiose by copper catalysts and its application to low-temperature depolymerization of cellulose

Fangwei Gu, Haichao Liu

Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Received:2019-12-08 Online:2020-07-18 Published:2020-04-18
Supported by:
This work was supported by the National Key Research and Development Program of China (2016YFB0701100), the Natural Science Foundation of China (21690081, 21433001, 21832001, 21821004), and Beijing National Laboratory for Molecular Sciences (BNLMS-CXXM-201905).

摘要/Abstract

摘要： 纤维素是葡萄糖通过β-1,4-糖苷键链接而成的高聚物,在木质纤维素中含量最高,结构稳定,较难水解.糖苷键的解聚主要有三种方式:酶水解、酸水解以及碱降解.酶解的优点是反应条件温和、副产物少,但存在成本高、活性低等缺点,限制了其大规模的工业化生产.碱水解纤维素的同时伴随着葡萄糖的peeling-off反应得到异变糖酸,需要消耗大量的碱,并且强碱也存在腐蚀性强和回收难等问题.酸水解是目前工业上常用的纤维素水解方法,在保持较高葡萄糖选择性的同时,通过对反应条件的控制(提高反应温度和酸浓度)来提高纤维素的水解效率,但是硫酸对设备的腐蚀性强,也难以回收,不符合绿色化学的发展要求.固体酸是近年来研究较多的纤维素水解催化剂.固体酸虽然腐蚀性弱、易回收,但是其活性低,水热稳定性较差,目前还不具备大规模生产的条件.本文发展了一种羟基自由基活化断裂糖苷键的方法,利用羟基自由基的高活性在低温下实现糖苷键的选择性断裂,同时羟基自由基与糖苷键作用后转化为无毒无害的水和氧气,将不会对环境造成污染.
我们首先以纤维二糖作为纤维素的模型分子,通过羟基自由基能够优先与糖苷键反应得到葡萄糖和葡萄糖酸的实验证实所提出的方法的可行性.实验表明,来自H₂O₂的·OH自由基能够在铜基催化剂作用下选择性氧化断裂其糖苷键,生成葡萄糖和葡萄糖酸.比如:采用均相CuSO₄体系,纤维二糖转化率约为20%时,葡萄糖和葡萄糖酸的选择性分别为28.5%和32.3%.采用多相CuO/SiO₂(4 wt% CuO)体系,纤维二糖转化率约为20%时,葡萄糖和葡萄糖酸的选择性约分别为23.3%和25.7%,并且该催化剂具有良好的循环使用性能.与·OH类似,CuSO₄催化过硫酸钾生成的·SO₄^-自由基也能够有效转化纤维二糖,在纤维二糖转化率为20%时,葡萄糖和葡萄糖酸的选择性分别为36.6%和39.9%.利用这种·OH和·SO₄^-自由基氧化的方法,也能够在较低温度下(333 K)解聚纤维素中的糖苷键.我们发展了H₂O₂浸渍预处理纤维浸渍预处理纤维素的方法,通过部分破坏纤维素糖苷键,提高了纤维素的水解活性.比如:处理后的纤维素在413 K条件下反应12 h,纤维素转化率和葡萄糖选择性分别达到约36.1%和42.5%.XRD结果表明,处理后的纤维素的晶体结构未发生明显的变化.FT-IR表征结果显示处理后的纤维素表面生成了大量的羧酸基团.

关键词: 纤维素解聚, 纤维二糖, 羟基自由基, 氧化断键, 糖苷键

Abstract: As the most abundant source of biomass in nature for sustainable production of fuels and chemicals, efficient depolymerization of cellulose under mild conditions, due to the difficulty in selective cleavage of its β-1,4-glycosidic bonds, still remains challenging. Here, we report a novel method for oxidative cleavage of the glycosidic bonds by free radicals. Probed by the cellobiose reaction, it was found that ·OH radicals, generated from the decomposition of H₂O₂ catalyzed by CuSO₄ or CuO/SiO₂, were efficient for selective conversion of cellobiose to glucose and gluconic acid at a low temperature of 333 K, and their selectivities reached 30.0% and 34.6%, respectively, at 23.4% cellobiose conversion. Other radicals, such as ·SO₄^-, also exhibited high efficacy in the cellobiose reaction. Mechanistic studies suggest that the oxidative cleavage of the β-1,4-glycosidic bond by the free radicals involve formation of the carbon radical intermediate via abstraction of the H atom dominantly at the C1 position. Following this oxidative mechanism, treatment of microcrystalline cellulose with ·OH by impregnation with H₂O₂ and CuSO4 catalyst at 343 K led to significant enhancement in its hydrolysis efficiency. These results demonstrate the effectiveness of this new method in the oxidative cleavage of glycosidic bonds, and its viability for the efficient depolymerization of cellulose at low temperatures, which can be further improved, for example, by exploring new free radicals and optimizing their reactivity and selectivity.

Key words: Cellulose depolymerization, Cellobiose, Hydroxyl radical, Oxidative cleavage, Glycosidic bond

顾方伟, 刘海超. Cu催化羟基自由基氧化断裂纤维二糖分子糖苷键反应及其在纤维素低温解聚中的应用[J]. 催化学报, 2020, 41(7): 1073-1080.

Fangwei Gu, Haichao Liu. Hydroxyl radicals-mediated oxidative cleavage of the glycosidic bond in cellobiose by copper catalysts and its application to low-temperature depolymerization of cellulose[J]. Chinese Journal of Catalysis, 2020, 41(7): 1073-1080.

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Cu催化羟基自由基氧化断裂纤维二糖分子糖苷键反应及其在纤维素低温解聚中的应用

Hydroxyl radicals-mediated oxidative cleavage of the glycosidic bond in cellobiose by copper catalysts and its application to low-temperature depolymerization of cellulose

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