Adsorption-Enhanced Hydrolysis of β-1,4-Glucan on Graphene-Based Amorphous Carbon Bearing SO3H, COOH, and OH Groups

被引:255
作者
Kitano, Masaaki [1 ]
Yamaguchi, Daizo [1 ]
Suganuma, Satoshi [2 ]
Nakajima, Kiyotaka [2 ]
Kato, Hideki [2 ]
Hayashi, Shigenobu [3 ]
Hara, Michikazu [1 ,2 ]
机构
[1] Kanagawa Acad Sci & Technol, Takatsu Ku, Kawasaki, Kanagawa 2130012, Japan
[2] Tokyo Inst Technol, Mat & Struct Lab, Midori Ku, Yokohama, Kanagawa 2268503, Japan
[3] Natl Inst Adv Ind Sci & Technol, Res Inst Instrumentat Frontier, Tsukuba, Ibaraki 3058565, Japan
基金
日本学术振兴会;
关键词
MOLECULAR-DYNAMICS; ACID CATALYSTS; NIOBIC ACID; ESTERIFICATION; CELLULOSE; ALCOHOL; BIOMASS;
D O I
10.1021/la8040506
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The reaction mechanism of the hydrolysis of cellulose by a carbon-based solid acid, amorphous carbon containing graphene sheets bearing SO3H, COOH, and phenolic OH groups, has been investigated in detail through the hydrolysis of water-soluble beta-1,4-glucan. Whereas a range of solid strong Bronsted acid catalysts (inorganic oxides with acidic OH groups, SO3H-bearing resins, and the carbon-based solid acid) can hydrolyze the beta-1,4-glycosidic bonds in cellobiose (the shortest water-soluble beta-1,4-glucan), the tested solid acids except for the carbon material, consisting of conventional solid acids, cannot function as effective catalysts for the hydrolysis of cellohexaose (a long-chain water-soluble beta-1,4-glucan). However, the carbon material exhibits remarkable catalytic performance for the hydrolysis of cellohexaose: the turnover frequency (TOF) of SO3H groups in the carbon material exceeds ca. 20 times those of the conventional solid acids, reaching that of sulfuric acid, which is the most active catalyst. Experimental results revealed that inorganic oxides with acidic OH groups are not acidic enough to decompose the hydrogen and beta-1,4-glycosidic bonds in cellohexaose molecules aggregated by strong hydrogen bonds as well as cellulose and that the SO3H groups of the resins that do not adsorb beta-1,4-glucan are unable to attack the hydrogen and beta-1,4-glycosidic bonds in cellohexaose molecules effectively. In contrast, the carbon material is capable of adsorbing beta-1,4-glucan by phenolic OH or COOH groups in the carbon material, and SO3H groups bonded to the carbon therefore function as effective active sites for both decomposing the hydrogen bonds and hydrolyzing the beta-1,4-glycosidic bonds in the adsorbed long-chain water-soluble beta-1,4-glucan aggregate. These results suggest that the synergetic combination of high densities of the functional groups bonded to amorphous carbon causes the efficient hydrolysis of beta-1,4-glucan, including cellulose, on the carbon material.
引用
收藏
页码:5068 / 5075
页数:8
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