Role of methoxy and C_(α)-based substituents in electrochemical oxidation mechanisms and bond cleavage selectivity of β-O-4 lignin model compounds

In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.

Radical and(photo)electron transfer induced mechanisms for lignin photo-and electro-catalytic depolymerization

As one of the three major components of woody biomass,lignin is a kind of natural organic polymer and the only abundant natural renewable resource with aromatic nucleus.Chemical catalysis induced depolymerization is an important and effective approach for lignin utilization.In particular,photocatalysis and electrocatalysis show great potential in accurately activating C-O/C-C bonds,which is a critical point of selective cleavage of lignin.In this contribution,we focus on radical and(photo)electron transfer induced reaction mechanisms of the photo(electro)catalytic depolymerization of lignin.Primarily,the general situation of Carbon-centered radicals and active oxygen species mediated lignin conversion has been discussed.Then the mechanisms for(photo)electron transfer mediated lignin depolymerization have been summarized.At the end of this review,the challenges and opportunities of photo(electro)catalysis in the applications of lignin valorization have been forecasted.

Selective photocatalytic aerobic oxidative cleavage of lignin C–O bonds over sodium lignosulfonate modified Fe_(3)O_(4)/TiO_(2)

Lignocellulose shows significantly potential in sustainable conversion to high-quality fuel and valueadded chemicals with the demands for realizing the rapid cycle of carbon resources and helping to reach carbon neutrality in nature.Selective tailoring of α-O-4,β-O-4,etc.linkages in lignin has always been viewed as "death blow" for its depolymerization.Herein,novel sodium lignosulfonate(SL) modified Fe_(3)O_(4)/TiO_(2)(SL-Fe_(3)O_(4)/TiO_(2)) spherical particles have been developed and used as catalysts for selectively photocatalytic oxidative cleavage of organosolv lignin.As expected,80% selective conversion of lignin in C2-C4 esters has been achieved,while C-O bonds in lignin model compounds can be effectively cleaved.Other than normal hydroxyl radical-mediated photocatalytic depolymerization of lignin over TiO_(2)-based materials,in this contribution,mechanism studies indicate that photogenerated holes and superoxide anion radicals are main active species,which trigger the cleavage of α/β-O-4 bond,and the isotopelabeling study confirms the crucial factor of C_β-H dehydrogenation in cleavage of β-O-4 bonds.

Combination Mechanism and Enhanced Visible-Light Photocatalytic Activity and Stability of CdS/g-C3N4 Heterojunctions

In this study, CdS/g-C3N4 （CSCN） heterojunctions were in situ fabricated with a large amount of CdS nanoparticles anchored on g-C3N4 nanosheets, A wet chemical method was developed for the first time to determine the actual content of CdS in CSCN composites. X-ray diffraction （XRD）, Fourier transform infrared spectra （FFIR）, high-resolution transmission electron microscopy （HRTEM） and UV-vis diffuse reflectance spectra （DRS） were employed to characterize the composition, structure and optical prop- erty of CSCN composites. Based on the is0electric point （liP） analysis of g-C3N4, a conclusion was obtained on the combination mechanism between CdS nanoparticles and g-C3N4 nanosheets. The photocatalytic activity of CSCN composites was much better than those of individual CdS and g-C3N4 for the degrada- tion of azo dye Methyl Orange （MO） by 40 min adsorption in the dark followed by 15 min photocatalysis under visible light irradiation. After 5 cycles, CSCN composites still maintained high reactive activity with the MO degradation efficiency of 93.8%, exhibiting good photocatalytic stability. The Cd2~ concentration dissolved in the supernatant detected by atomic absorption spectroscopy （AAS） of CSCN composites was lower than that of pure CdS, implying that the photocorrosion of CdS could be suppressed via the combination with g-C3N4. Photoluminescence emission spectra （PL） results clearly revealed that the recombination of photogenerated electron-hole pairs in CSCN composites was effectively inhibited due to the formation of heterojunctions. Based on the band alignments of g-C3N4 and CdS, the possible photocatalvtic mechnism was discussed.

厌氧微生物培养分离:过去、现在和未来

厌氧菌是地球上数量最多、物种最丰富的微生物,也是分类上报道最少的微生物。它们对氧气敏感、生长条件苛刻,不容易培养分离。本文简要总结了厌氧微生物的研究历史,分析了限制厌氧微生物培养分离的主要因素,讨论了厌氧微生物培养分离的策略和方法,回顾了国内外厌氧微生物的系统分类学现状,并展望了厌氧微生物培养分离的发展趋势。

Determination of perchlorate and its distribution in unhusked rice in China

Perchlorate concentrations in 387 unhusked rice samples from 15 main producing provinces/municipality in China were investigated by high-performance liquid chromatography-tanden mass spectrometry.The results indicated that perchlorate displays a mean level of 17.17μg/kg in un-husked rice samples.Intriguingly,we also found that perchlorate is mainly observed in rice husk among these collected unhusked rice samples,while less observed in rice bran and milled rice.Specifically,the perchlorate levels in rice were found in the husks(73.61%),bran(10.09%),and milled rice(19.52%),respectively.Our results indicated that there is no significantly perchlorate exposure risk in edible milled rice.

催化生物质高效转化过程耦合与强化

生物质是自然界中唯一可再生含碳资源且年产量巨大,将其高效转化与利用,契合“双碳”目标.但生物质的化学转化存在条件苛刻、产物分布广、高值化产品选择性低等瓶颈问题.结合课题组的科研成果,本文基于生物质本征结构特征,结合高效解聚催化过程的设计,从溶解、催化、反应、产物分离等多角度出发,创新催化生物质高效定向转化过程耦合与强化技术模式,并在生物质高效转化新路径、转化过程耦合与强化作用机制等方面进行阐释;同时,对催化过程耦合多场作用改善生物质定向转化效率与拓展生物质高效利用路径进行了展望,期望为生物质高效转化领域的相关研究提供理论基础与技术支撑.