The microwave assisted liquefaction process of wheat straw alkali lignin was investigated to obtain monophenolic compounds as the precursor of bio-fuel. It is found that the total yield of monophenolic compounds is si...The microwave assisted liquefaction process of wheat straw alkali lignin was investigated to obtain monophenolic compounds as the precursor of bio-fuel. It is found that the total yield of monophenolic compounds is significantly improved under microwave irradiation, reaching 15.77% under a relatively mild liquefaction condition of 10 wt% H2SO4 as the catalyst, 10 wt% phenol as the hydrogen-donor reagent at 120 ℃ for 40 rain. Compared with conventional thermal liquefaction process, microwave irradiation promotes the cleavage of C-C bonds, which gives an extra 29% of Caryl-Cα bond cleavage, and increases the yield of monophenolic compounds from 0.92% to 13.61% under the same conditions. The excessive temperature and prolonged time under microwave irradiation will promote the recondensation of degraded lignin fragments, so the key to obtain high yield of monophenolic compounds is to avoid the recondensation reaction. The selected solid catalyst promotes the dissociation of methoxy groups, and the addition of phenol into liquefaction can only slightly improve the yield of monophencolic compounds.展开更多
Photocatalytic selective transform native lignin into valuable chemicals is an attractive but challenging task.Herein,we report a mesoporous sulfur-doped carbon nitride(MSCN-0.5)which is prepared by a facile one-step ...Photocatalytic selective transform native lignin into valuable chemicals is an attractive but challenging task.Herein,we report a mesoporous sulfur-doped carbon nitride(MSCN-0.5)which is prepared by a facile one-step thermal condensation strategy.It is highly active and selective for the cleavage Cα-Cβbond inβ-O-4 lignin model compound under visible light radiation at room temperature,achieving 99%substrate conversion and 98%Cα-Cβbond cleavage selectivity.Mechanistic studies revealed that the Cβ-H bond of lignin model compounds activated by holes and generate key Cβradical intermediates,further induced the Cα-Cβbond cleavage by superoxide anion radicals(·O2-)to produce aromatic oxygenates.Waste Camellia oleifera shell(WCOS)was taken as a representative to further understand the reaction mechanisms on native lignin.33.2 mg of monophenolic compounds(Vanillin accounted for 22%and Syringaldehyde for 34%)can be obtained by each gram of WCOS lignin,which is 2.5 times as that of the pristine carbon nitride.The present work offers useful guidance for designing metal-free heterogeneous photocatalysts for Cα-Cβbond cleavage to harvest monophenolic compounds.展开更多
基金supported by the National Basic Research Program of China(2012CB215302)Guangdong Provincial Natural Science Fund(9151064101000082)
文摘The microwave assisted liquefaction process of wheat straw alkali lignin was investigated to obtain monophenolic compounds as the precursor of bio-fuel. It is found that the total yield of monophenolic compounds is significantly improved under microwave irradiation, reaching 15.77% under a relatively mild liquefaction condition of 10 wt% H2SO4 as the catalyst, 10 wt% phenol as the hydrogen-donor reagent at 120 ℃ for 40 rain. Compared with conventional thermal liquefaction process, microwave irradiation promotes the cleavage of C-C bonds, which gives an extra 29% of Caryl-Cα bond cleavage, and increases the yield of monophenolic compounds from 0.92% to 13.61% under the same conditions. The excessive temperature and prolonged time under microwave irradiation will promote the recondensation of degraded lignin fragments, so the key to obtain high yield of monophenolic compounds is to avoid the recondensation reaction. The selected solid catalyst promotes the dissociation of methoxy groups, and the addition of phenol into liquefaction can only slightly improve the yield of monophencolic compounds.
基金finacially supported by the National Natural Science Foundation of China(Nos.21966023,21665018 and 51568049)the Natural Science Foundation of Jiangxi Province,China(No.20171ACB21035)Jiangxi Province Graduate Student Innovation Special Fund(No.YC2020-S513)。
文摘Photocatalytic selective transform native lignin into valuable chemicals is an attractive but challenging task.Herein,we report a mesoporous sulfur-doped carbon nitride(MSCN-0.5)which is prepared by a facile one-step thermal condensation strategy.It is highly active and selective for the cleavage Cα-Cβbond inβ-O-4 lignin model compound under visible light radiation at room temperature,achieving 99%substrate conversion and 98%Cα-Cβbond cleavage selectivity.Mechanistic studies revealed that the Cβ-H bond of lignin model compounds activated by holes and generate key Cβradical intermediates,further induced the Cα-Cβbond cleavage by superoxide anion radicals(·O2-)to produce aromatic oxygenates.Waste Camellia oleifera shell(WCOS)was taken as a representative to further understand the reaction mechanisms on native lignin.33.2 mg of monophenolic compounds(Vanillin accounted for 22%and Syringaldehyde for 34%)can be obtained by each gram of WCOS lignin,which is 2.5 times as that of the pristine carbon nitride.The present work offers useful guidance for designing metal-free heterogeneous photocatalysts for Cα-Cβbond cleavage to harvest monophenolic compounds.
