The oxidation of lignin model compounds to esters via C-C bond cleavage has attracted considerable attention,as esters could be used as important polymer precursors and pharmaceutical intermediates.However,most studie...The oxidation of lignin model compounds to esters via C-C bond cleavage has attracted considerable attention,as esters could be used as important polymer precursors and pharmaceutical intermediates.However,most studies focus on designing homogeneous or noble metal catalysts and conducting the reactions under basic conditions.Here,we report an efficient process for the C-C bond cleavage of lignin model compounds and selectively producing esters over different shaped CeO_(2)(i.e.,nanospheres(S),nanorods(R),nanoparticles(P),and nanocubes(C))under base-free conditions.Specifically,the yield of methyl anisate from the aerobic oxidation of l-(4-methoxyphenyl)ethanol reaches 77.6%over CeO_(2)-S in one hour(91%in 9 h),exhibiting higher performance compared to other evaluated CeO_(2)catalysts(6.4%-40.2%).Extensivecharacterizations and experimental investigations reveal that the density of weak base sites and oxygen vacancies on the CeO_(2)surface is positively correlated with the yield of methyl esters.Furthermore,the reaction pathway is investigated,which confirms that 1-(4-methoxyphenyl)ethanol first undergoes two reactions(i.e.,etherification and dehydrogenation)to produce intermediates of1-methoxy-4-(1-methoxy-ethyl)-benzene and 1-(4-methoxyphenyl)ethanone,respectively,followed by a series of functional group transformations to generate the targeted methyl anisate ultimately.展开更多
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 gro...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.展开更多
Six model compounds have been synthesized and used for probing the structural features of the Mn cluster in oxygen_evolving complex (OEC) of photosystem Ⅱ (PSⅡ). The model compounds contain Mn 2(μ_O) 2 and μ_O_...Six model compounds have been synthesized and used for probing the structural features of the Mn cluster in oxygen_evolving complex (OEC) of photosystem Ⅱ (PSⅡ). The model compounds contain Mn 2(μ_O) 2 and μ_O_μ_carboxylato di_manganese structural units, which offer Mn—Mn, Mn……Mn, and Mn—O(N) structural parameters consistent with the corresponding data of the OEC in PSⅡ, implying that the Mn cluster in OEC may possess similar structural features. Two model compounds containing halide anion have been used for discussing the binding of Cl - to Mn in PSⅡ. It is suggested that in the five S states, ligand exchange would lead to the ligation of chloride to Mn in the S states with Mn of higher valence.展开更多
Three compounds modeled on the lignite structure were chosen for experimental degradation by different fungi strains. Culture conditions and extracellular enzyme activities were optimized. The growth curves of the str...Three compounds modeled on the lignite structure were chosen for experimental degradation by different fungi strains. Culture conditions and extracellular enzyme activities were optimized. The growth curves of the strains were determined to study mycelium dry weight and protein content changes. Gas chromatography and infrared spectroscopy were used to detect changes of functional groups before and after the action of the fungi on the model compounds. Possible decomposition products and degrada-tion mechanisms were proposed. The research findings show that C. Versicolor and Golden Mushroom can grow in presence of the model compounds. The optimum culture conditions were a pH of 6.0, a carbon-nitrogen ratio of five and a Tween-80 concentration of 0.1%. Newly produced substances were found by gas chromatography. Infrared analysis showed that the model compounds degraded under the action of the microorganisms.展开更多
The steam reforming of four bio-oil model compounds（acetic acid,ethanol,acetone and phenol） was investigated over Ni-based catalysts supported on Al2O3 modified by Mg,Ce or Co in this paper.The activation process ca...The steam reforming of four bio-oil model compounds（acetic acid,ethanol,acetone and phenol） was investigated over Ni-based catalysts supported on Al2O3 modified by Mg,Ce or Co in this paper.The activation process can improve the catalytic activity with the change of high-valence Ni（Ni2O3,NiO） to low-valence Ni（Ni,NiO）.Among these catalysts after activation,the Ce-Ni/Co catalyst showed the best catalytic activity for the steam reforming of all the four model compounds.After long-term experiment at 700°C and the S/C ratio of 9,the Ce-Ni/Co catalyst still maintained excellent stability for the steam reforming of the simulated bio-oil（mixed by the four compounds with the equal masses）.With CaO calcinated from calcium acetate as CO2 sorbent,the catalytic steam reforming experiment combined with continuous in situ CO2 adsorption was performed.With the comparison of the case without the adding of CO2 sorbent,the hydrogen concentration was dramatically improved from 74.8% to 92.3%,with the CO2 concentration obviously decreased from 19.90% to 1.88%.展开更多
As a natural aromatic polymer,lignin has great potential but limited industrial application due to its complex chemical structure.Among strategies for lignin conversion,biodegradation has attracted promising interest ...As a natural aromatic polymer,lignin has great potential but limited industrial application due to its complex chemical structure.Among strategies for lignin conversion,biodegradation has attracted promising interest recently in term of efficiency,selectivity and mild condition.In order to overcome the issues of poor stability and non-reusability of enzyme in the biodegradation of lignin,this work explored a protocol of immobilized laccase on magnetic nanoparticles(MNPs)with rough surfaces for enhanced lignin model compounds degradation.Scanning electron microscope with energy dispersive spectrometer(SEM-EDS),flourier transformation infrared spectroscopy(FTIR)and thermal gravimetric analysis(TGA)were utilized to characterize the immobilization of laccase.The results showed a maximum activity recovery of 64.7%towards laccase when it was incubated with MNPs and glutaraldehyde(GA)with concentrations of 6 mg·ml^-1and 7.5 mg·ml^-1for 5 h,respectively.The immobilized laccase showed improved thermal stability and pH tolerance compared with free laccase,and remained more than 80%of its initial activity after 20 days of storage at 4℃.In addition,about 40%residual activity of the laccase remained after 8 times cycles.Gas chromatography–mass spectrometry(GC–MS)was utilized to characterize the products of lignin model compound degradation and activation,and the efficiency of immobilized laccase was calculated to be 1–5 times that of free laccase.It was proposed that the synergistic effect between MNPs and laccase displays an important role in the enhancement of stability and activity in lignin model compound biodegradation.展开更多
B3LYP/6-31G(d,p) method was used to investigate the catalytic cracking mechanism of biomass tar model compound.Phenol,toluene and benzene were selected as the tar model compounds and CaO was selected as the catalyst.T...B3LYP/6-31G(d,p) method was used to investigate the catalytic cracking mechanism of biomass tar model compound.Phenol,toluene and benzene were selected as the tar model compounds and CaO was selected as the catalyst.The pathways of tar compound radical absorbed by CaO were determined firstly through comparing enthalpy changes of the absorption,and then Mulliken population changes were analyzed.The results show that the absorption of tar model compound radical and CaO is an exothermic reaction.Formation of C—O—Ca is more easily than that of C—Ca—O and formation of Caromatic—Caromatic—Ca—O is more easily than that of Caromatic—C(O)—Ca—O.The C—C bond Mulliken populations in tar model compound radicals are reduced by 11.9%,10.5% and 15.5% in the case of a hydrogen atom removed,and those are 15.7%,14.3% and 16.3% in the case of two hydrogen atoms removed through the absorption of CaO.Catalytic ability of CaO acting on the tar model compound is in an order of phenol>benzene>toluene.展开更多
Electrolytic reductions of oxygenic functional groups （OFGs） on coal surface and coal model compounds with OFGs in an aqueous NaCl solution are studied by electrochemical methods combined with GC/MS, GC and FFIR ana...Electrolytic reductions of oxygenic functional groups （OFGs） on coal surface and coal model compounds with OFGs in an aqueous NaCl solution are studied by electrochemical methods combined with GC/MS, GC and FFIR analyses. Different electrode reactions, their corresponding potentials and dynamic equations during the processes are investigated. The results show that benzoic acid, benzaldehyde, benzalcohol and hypnone are reduced to benzaldehyde and benzalcohol, methoxybenzene and benzal- cohol, toluene and styrene, respectively, at the cathode. The corresponding electrode potentials and dynamic equations are deter- mined. The.electrolytic reduction also leads to an increase in the contents of hydroxyl groups and aliphatic moieties and a corresponding decrease in those of carboxyl and carbonyl groups in Nantong coal, a high-sulfur coal, an enhancement in the flotation desulfurization of the coal. ER also reduces organic sulfur and FeS2 in the coal.展开更多
This paper establishes a new model for calculation of the standard entropies of solid binary oxides as follows: S_(29)=27.07×Φ_1+1.120×Φ_2+n_1×k×Φ, -22.19 e.u (R=0.9960) We have invesigated 103 ...This paper establishes a new model for calculation of the standard entropies of solid binary oxides as follows: S_(29)=27.07×Φ_1+1.120×Φ_2+n_1×k×Φ, -22.19 e.u (R=0.9960) We have invesigated 103 binary oxides. and found good agreemenl between estimated and experimental entropies.展开更多
Production o f aromatics from lignin has attracted much attention. Because of the coexistence of C-O and C-C bonds and their complex combinations in the lignin macromolecular network, a plausible roadmap for de...Production o f aromatics from lignin has attracted much attention. Because of the coexistence of C-O and C-C bonds and their complex combinations in the lignin macromolecular network, a plausible roadmap for developing a lignin catalytic decomposition process could be developed by exploring the transformation mechanisms of various model compounds. Herein, decomposition of a lignin model compound, 2-phenoxyacetophenone （2-PAP）, was investigated over several ce-sium-exchanged polyoxometalate （Cs-POM） catalysts. Decomposition of 2-PAP can follow two dif-ferent mechanisms： an active hydrogen transfer mechanism or an oxonium cation mechanism. The mechanism for most reactions depends on the competition between the acidity and redox proper-ties of the catalysts. The catalysts of POMs perform the following functions： promoting active hy-drogen liberated from ethanol and causing formation of and then temporarily stabilizing oxonium cations from 2-PAP. The use of Cs-PMo, which with strong redox ability, enhances hydrogen libera-tion and promotes liberated hydrogen transfer to the reaction intermediates. As a consequence, complete conversion of 2-PAP （〉99%） with excellent selectivities to the desired products （98.6% for phenol and 91.1% for acetophenone） can be achieved.展开更多
Consider two dependent renewal risk models with constant interest rate. By using some methods in the risk theory, uniform asymptotics for finite-time ruin probability is derived in a non-compound risk model, where cla...Consider two dependent renewal risk models with constant interest rate. By using some methods in the risk theory, uniform asymptotics for finite-time ruin probability is derived in a non-compound risk model, where claim sizes are upper tail asymptotically independent random variables with dominatedly varying tails, claim inter-arrival times follow the widely lower orthant dependent structure, and the total amount of premiums is a nonnegative stochastic process. Based on the obtained result, using the method of analysis for the tail probability of random sums, a similar result in a more complex and reasonable compound risk model is also obtained, where individual claim sizes are specialized to be extended negatively dependent and accident inter-arrival times are still widely lower orthant dependent, and both the claim sizes and the claim number have dominatedly varying tails.展开更多
Green and atom-economic depolymerization of lignin remains a great challenge due toits complex non-repetitive structure and the inert property for chemo-digestion. A redoxneutrallignin depolymerization system without ...Green and atom-economic depolymerization of lignin remains a great challenge due toits complex non-repetitive structure and the inert property for chemo-digestion. A redoxneutrallignin depolymerization system without the use of extra oxidant and/or reductantover a Co-NC catalyst has been developed in this work, providing the first non-noble metalheterogeneous catalytic system for redox-neutral valorization of lignin. Mechanistic studiesbased on control reactions and deuterium labeling experiments suggest that the reactionproceeds via ametal-catalyzed dehydrogenation of C_(α)-OH to afford a carbonyl intermediate,followed by C_(β)-O bond cleavage (via hydrogenolysis) to afford monophenols and aromaticketone products. The hydrogen used for the cleavage of the C_(β)-O bond originates from thealcoholmoiety in the substrate, and the cascade dehydrogenation and hydrogenolysis stepsare highly coupled, rendering it an efficient and atom-economic process.展开更多
N-participated lignin depolymerization is of great importance for the transformation of waste lignin into value-added chemicals.The vast majority of developed strategies employ organic amines as nitrogen source,and co...N-participated lignin depolymerization is of great importance for the transformation of waste lignin into value-added chemicals.The vast majority of developed strategies employ organic amines as nitrogen source,and considerablemethods rely on excessive use of strong base,which suffers severe environmental issues.Herein,benzonitrile derivatives are synthesized from oxidized ligninβ-O-4 model compounds in the presence of solid nitrogen source(NH_(4))_(2)CO_(3)under mild,base-free conditions over commercially available copper catalyst.Mechanism studies suggest the transformation undergoes a one-pot,highly coupled cascade reaction path involving oxidative C-C bond cleavage and in-situ formation of C≡N bond.Of which,Cu(OAc)2 catalyzes the transfer of hydrogen from C_(β)(C_(β)-H)to C_(α),leading to the cleavage of C_(α)-C_(β)bonds to offer benzaldehyde derivative,this intermediate then reacts in-situ with(NH_(4))_(2)CO_(3)to afford the targeted aromatic nitrile product.Tetrabutylammonium iodide(TBAI),acting as a promoter,plays a key role in breaking the C_(α)-C_(β)bonds to form the intermediate benzaldehyde derivative.With this protocol,the feasibility of the production of value-added syringonitrile from birchwood lignin has been demonstrated.This transformation provides a sustainable approach to benzonitrile chemicals from renewable source of lignin.展开更多
Heterogeneous precious metal catalysts are prone to agglomeration during preparation,requiring high usage with consequently high costs.Maximizing the efficiency of precious-metal utilization is of great significance i...Heterogeneous precious metal catalysts are prone to agglomeration during preparation,requiring high usage with consequently high costs.Maximizing the efficiency of precious-metal utilization is of great significance in the design of supported precious metal catalysts.Herein,2,2'-bipyridyl-5,5'-dicarboxylic acid was used as the ligand in constructing the UiO-67-Ce-BPyDC framework with Ce^(4+)coordination.This framework enables precise adsorption and coordination of Pd2+at the nitrogen sites of pyridine,promoting high dispersion of the Pd species at a single site,thereby facilitating controlled palladium loading.This precursor was used to fabricate supported Pd-based catalysts on CeO_(2)(Pd-N/CeO_(2)-P)via pyrolysis.Notably,because the Pd species are homogeneously distributed on CeO_(2)with strong interactions,Pd-N/CeO_(2)-P exhibits remarkable efficiency in cleaving the C-O bonds of diphenyl ether(DPE)to produce cyclohexanol,with a selectivity of 72.1%.The origin of the high selectivity of cyclohexanol is further elucidated using theoretical calculations;that is,DPE undergoes not only hydrogenolysis on Pd-N/CeO_(2)-P,but also hydrolysis to produce more cyclohexanol.This study not only demonstrates a successful strategy for designing highly dispersed metal catalysts,but also underscores the importance of such tailored catalysts in the advancement of sustainable lignin depolymerization technologies.展开更多
In this paper, a compound binomial model with a constant dividend barrier and random income is considered. Two types of individual claims, main claims and by-claims, are defined, where every by-claim is induced by the...In this paper, a compound binomial model with a constant dividend barrier and random income is considered. Two types of individual claims, main claims and by-claims, are defined, where every by-claim is induced by the main claim and may be delayed for one time period with a certain probability. The premium income is assumed to another binomial process to capture the uncertainty of the customer＇s arrivals and payments. A system of difference equations with certain boundary conditions for the expected present value of total dividend payments prior to ruin is derived and solved. Explicit results are obtained when the claim sizes are Kn distributed or the claim size distributions have finite support. Numerical results are also provided to illustrate the impact of the delay of by-claims on the expected present value of dividends.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
The reaction characteristics of phenolic hydroxyl group were studied under the conditions of direct coal liquefaction. 2-naphthol was used as a coal model compound in this study. Under the conditions of with and witho...The reaction characteristics of phenolic hydroxyl group were studied under the conditions of direct coal liquefaction. 2-naphthol was used as a coal model compound in this study. Under the conditions of with and without catalysts, a series of experiments were conducted at different temperatures, pressures and reaction time. Gas chromatography-mass spectrometry and gas chromatography were used to identify and quantify the reactants and products respectively. The conversion of 2-naphthol rises with the increase of reaction temperature, initial pressure and catalyst amount. The results indicated that tem- perature had a significant effect on 2-naphthol conversion, which promoted the dehydroxylation reaction. However, initial pressure had an important influence on the hydrogenation of 2-naphthol and naphthalene. The iron catalyst plays a significant role of cracking instead of hydrogenation. It is concluded that the harsh reaction conditions of high temperature, high pressure, and more catalyst are conducive to promoting dehydroxylation of 2-naphthol. The reaction mechanism was put forward based the experimental results, in which 2-tetralone was an intermediate.展开更多
Building façades can feature different patterns depending on the architectural style,function-ality,and size of the buildings;therefore,reconstructing these façades can be complicated.In particular,when sema...Building façades can feature different patterns depending on the architectural style,function-ality,and size of the buildings;therefore,reconstructing these façades can be complicated.In particular,when semantic façades are reconstructed from point cloud data,uneven point density and noise make it difficult to accurately determine the façade structure.When inves-tigating façade layouts,Gestalt principles can be applied to cluster visually similar floors and façade elements,allowing for a more intuitive interpretation of façade structures.We propose a novel model for describing façade structures,namely the layout graph model,which involves a compound graph with two structure levels.In the proposed model,similar façade elements such as windows are first grouped into clusters.A down-layout graph is then formed using this cluster as a node and by combining intra-and inter-cluster spacings as the edges.Second,a top-layout graph is formed by clustering similar floors.By extracting relevant parameters from this model,we transform semantic façade reconstruction to an optimization strategy using simulated annealing coupled with Gibbs sampling.Multiple façade point cloud data with different features were selected from three datasets to verify the effectiveness of this method.The experimental results show that the proposed method achieves an average accuracy of 86.35%.Owing to its flexibility,the proposed layout graph model can deal with different types of façades and qualities of point cloud data,enabling a more robust and accurate reconstruc-tion of façade models.展开更多
This article deals with the problem of minimizing ruin probability under optimal control for the continuous-time compound binomial model with investment. The jump mechanism in our article is different from that of Liu...This article deals with the problem of minimizing ruin probability under optimal control for the continuous-time compound binomial model with investment. The jump mechanism in our article is different from that of Liu et al [4]. Comparing with [4], the introduction of the investment, and hence, the additional Brownian motion term, makes the problem technically challenging. To overcome this technical difficulty, the theory of change of measure is used and an exponential martingale is obtained by virtue of the extended generator. The ruin probability is minimized through maximizing adjustment coefficient in the sense of Lundberg bounds. At the same time, the optimal investment strategy is obtained.展开更多
基金financially supported by the National Key Research and Development Program of China(No.2023YFD2200505)the National Natural Science Foundation of China(No.22202105)+3 种基金the Natural Science Foundation of Jiangsu Higher Education Institutions of China(No.21KJA150003)the Innovation and Entrepreneurship Team Program of Jiangsu Province(No.JSSCTD202345)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX23_1163)the China Postdoctoral Science Foundation(Nos.2023M731703 and 2024T170415)
文摘The oxidation of lignin model compounds to esters via C-C bond cleavage has attracted considerable attention,as esters could be used as important polymer precursors and pharmaceutical intermediates.However,most studies focus on designing homogeneous or noble metal catalysts and conducting the reactions under basic conditions.Here,we report an efficient process for the C-C bond cleavage of lignin model compounds and selectively producing esters over different shaped CeO_(2)(i.e.,nanospheres(S),nanorods(R),nanoparticles(P),and nanocubes(C))under base-free conditions.Specifically,the yield of methyl anisate from the aerobic oxidation of l-(4-methoxyphenyl)ethanol reaches 77.6%over CeO_(2)-S in one hour(91%in 9 h),exhibiting higher performance compared to other evaluated CeO_(2)catalysts(6.4%-40.2%).Extensivecharacterizations and experimental investigations reveal that the density of weak base sites and oxygen vacancies on the CeO_(2)surface is positively correlated with the yield of methyl esters.Furthermore,the reaction pathway is investigated,which confirms that 1-(4-methoxyphenyl)ethanol first undergoes two reactions(i.e.,etherification and dehydrogenation)to produce intermediates of1-methoxy-4-(1-methoxy-ethyl)-benzene and 1-(4-methoxyphenyl)ethanone,respectively,followed by a series of functional group transformations to generate the targeted methyl anisate ultimately.
基金The authors gratefully acknowledge the financial support of the Natural Science Foundation of China,China(Grant No.21975082 and 21736003)the Guangdong Basic and Applied Basic Research Foundation(Grant Number:2019A1515011472 and 2022A1515011341)the Science and Technology Program of Guangzhou(Grant Number:202102080479).
文摘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.
基金The State Key Basic Research and Development Plan(G1998010100)the National Natural Science Foundation of China(29733090,29973047,39970177)
文摘Six model compounds have been synthesized and used for probing the structural features of the Mn cluster in oxygen_evolving complex (OEC) of photosystem Ⅱ (PSⅡ). The model compounds contain Mn 2(μ_O) 2 and μ_O_μ_carboxylato di_manganese structural units, which offer Mn—Mn, Mn……Mn, and Mn—O(N) structural parameters consistent with the corresponding data of the OEC in PSⅡ, implying that the Mn cluster in OEC may possess similar structural features. Two model compounds containing halide anion have been used for discussing the binding of Cl - to Mn in PSⅡ. It is suggested that in the five S states, ligand exchange would lead to the ligation of chloride to Mn in the S states with Mn of higher valence.
基金Financial support for this research, provided by the National Natural Science Foundation of China (Nos.50874107, 50921002 and 50374068)the Key Laboratory of Coal Processing & Efficient Utilization Foundation of Ministry of Education of China (No.CPEUKF06-12), are gratefully acknowl-edged
文摘Three compounds modeled on the lignite structure were chosen for experimental degradation by different fungi strains. Culture conditions and extracellular enzyme activities were optimized. The growth curves of the strains were determined to study mycelium dry weight and protein content changes. Gas chromatography and infrared spectroscopy were used to detect changes of functional groups before and after the action of the fungi on the model compounds. Possible decomposition products and degrada-tion mechanisms were proposed. The research findings show that C. Versicolor and Golden Mushroom can grow in presence of the model compounds. The optimum culture conditions were a pH of 6.0, a carbon-nitrogen ratio of five and a Tween-80 concentration of 0.1%. Newly produced substances were found by gas chromatography. Infrared analysis showed that the model compounds degraded under the action of the microorganisms.
基金supported by the National Natural Science Foundation of China(No.51274066,51304048)the National Key Technology R&D Program of China(No.2013BAA03B03)the National Science Foundation for Post-doctoral Scientists of China(No.2013M541240)
文摘The steam reforming of four bio-oil model compounds（acetic acid,ethanol,acetone and phenol） was investigated over Ni-based catalysts supported on Al2O3 modified by Mg,Ce or Co in this paper.The activation process can improve the catalytic activity with the change of high-valence Ni（Ni2O3,NiO） to low-valence Ni（Ni,NiO）.Among these catalysts after activation,the Ce-Ni/Co catalyst showed the best catalytic activity for the steam reforming of all the four model compounds.After long-term experiment at 700°C and the S/C ratio of 9,the Ce-Ni/Co catalyst still maintained excellent stability for the steam reforming of the simulated bio-oil（mixed by the four compounds with the equal masses）.With CaO calcinated from calcium acetate as CO2 sorbent,the catalytic steam reforming experiment combined with continuous in situ CO2 adsorption was performed.With the comparison of the case without the adding of CO2 sorbent,the hydrogen concentration was dramatically improved from 74.8% to 92.3%,with the CO2 concentration obviously decreased from 19.90% to 1.88%.
基金supported by the Startup Foundation of Beijing Institute of Technology,China(3160011181808)。
文摘As a natural aromatic polymer,lignin has great potential but limited industrial application due to its complex chemical structure.Among strategies for lignin conversion,biodegradation has attracted promising interest recently in term of efficiency,selectivity and mild condition.In order to overcome the issues of poor stability and non-reusability of enzyme in the biodegradation of lignin,this work explored a protocol of immobilized laccase on magnetic nanoparticles(MNPs)with rough surfaces for enhanced lignin model compounds degradation.Scanning electron microscope with energy dispersive spectrometer(SEM-EDS),flourier transformation infrared spectroscopy(FTIR)and thermal gravimetric analysis(TGA)were utilized to characterize the immobilization of laccase.The results showed a maximum activity recovery of 64.7%towards laccase when it was incubated with MNPs and glutaraldehyde(GA)with concentrations of 6 mg·ml^-1and 7.5 mg·ml^-1for 5 h,respectively.The immobilized laccase showed improved thermal stability and pH tolerance compared with free laccase,and remained more than 80%of its initial activity after 20 days of storage at 4℃.In addition,about 40%residual activity of the laccase remained after 8 times cycles.Gas chromatography–mass spectrometry(GC–MS)was utilized to characterize the products of lignin model compound degradation and activation,and the efficiency of immobilized laccase was calculated to be 1–5 times that of free laccase.It was proposed that the synergistic effect between MNPs and laccase displays an important role in the enhancement of stability and activity in lignin model compound biodegradation.
基金Project(51276023)supported by the National Natural Science Foundation of China
文摘B3LYP/6-31G(d,p) method was used to investigate the catalytic cracking mechanism of biomass tar model compound.Phenol,toluene and benzene were selected as the tar model compounds and CaO was selected as the catalyst.The pathways of tar compound radical absorbed by CaO were determined firstly through comparing enthalpy changes of the absorption,and then Mulliken population changes were analyzed.The results show that the absorption of tar model compound radical and CaO is an exothermic reaction.Formation of C—O—Ca is more easily than that of C—Ca—O and formation of Caromatic—Caromatic—Ca—O is more easily than that of Caromatic—C(O)—Ca—O.The C—C bond Mulliken populations in tar model compound radicals are reduced by 11.9%,10.5% and 15.5% in the case of a hydrogen atom removed,and those are 15.7%,14.3% and 16.3% in the case of two hydrogen atoms removed through the absorption of CaO.Catalytic ability of CaO acting on the tar model compound is in an order of phenol>benzene>toluene.
基金Project 2004CB217601 supported by the Special Fund for Major State Basic Research Projects
文摘Electrolytic reductions of oxygenic functional groups （OFGs） on coal surface and coal model compounds with OFGs in an aqueous NaCl solution are studied by electrochemical methods combined with GC/MS, GC and FFIR analyses. Different electrode reactions, their corresponding potentials and dynamic equations during the processes are investigated. The results show that benzoic acid, benzaldehyde, benzalcohol and hypnone are reduced to benzaldehyde and benzalcohol, methoxybenzene and benzal- cohol, toluene and styrene, respectively, at the cathode. The corresponding electrode potentials and dynamic equations are deter- mined. The.electrolytic reduction also leads to an increase in the contents of hydroxyl groups and aliphatic moieties and a corresponding decrease in those of carboxyl and carbonyl groups in Nantong coal, a high-sulfur coal, an enhancement in the flotation desulfurization of the coal. ER also reduces organic sulfur and FeS2 in the coal.
文摘This paper establishes a new model for calculation of the standard entropies of solid binary oxides as follows: S_(29)=27.07×Φ_1+1.120×Φ_2+n_1×k×Φ, -22.19 e.u (R=0.9960) We have invesigated 103 binary oxides. and found good agreemenl between estimated and experimental entropies.
基金supported by the National Key Basic Research Program of China(973 program,2013CB934101)National Natural Science Foundation of China(21433002,21573046)+1 种基金China Postdoctoral Science Foundation(2016M601492)International Science and Technology Cooperation Projects of Guangxi(15104001-5)~~
文摘Production o f aromatics from lignin has attracted much attention. Because of the coexistence of C-O and C-C bonds and their complex combinations in the lignin macromolecular network, a plausible roadmap for developing a lignin catalytic decomposition process could be developed by exploring the transformation mechanisms of various model compounds. Herein, decomposition of a lignin model compound, 2-phenoxyacetophenone （2-PAP）, was investigated over several ce-sium-exchanged polyoxometalate （Cs-POM） catalysts. Decomposition of 2-PAP can follow two dif-ferent mechanisms： an active hydrogen transfer mechanism or an oxonium cation mechanism. The mechanism for most reactions depends on the competition between the acidity and redox proper-ties of the catalysts. The catalysts of POMs perform the following functions： promoting active hy-drogen liberated from ethanol and causing formation of and then temporarily stabilizing oxonium cations from 2-PAP. The use of Cs-PMo, which with strong redox ability, enhances hydrogen libera-tion and promotes liberated hydrogen transfer to the reaction intermediates. As a consequence, complete conversion of 2-PAP （〉99%） with excellent selectivities to the desired products （98.6% for phenol and 91.1% for acetophenone） can be achieved.
基金The National Natural Science Foundation of China(No.11001052,11171065,71171046)China Postdoctoral Science Foundation(No.2012M520964)+1 种基金the Natural Science Foundation of Jiangsu Province(No.BK20131339)the Qing Lan Project of Jiangsu Province
文摘Consider two dependent renewal risk models with constant interest rate. By using some methods in the risk theory, uniform asymptotics for finite-time ruin probability is derived in a non-compound risk model, where claim sizes are upper tail asymptotically independent random variables with dominatedly varying tails, claim inter-arrival times follow the widely lower orthant dependent structure, and the total amount of premiums is a nonnegative stochastic process. Based on the obtained result, using the method of analysis for the tail probability of random sums, a similar result in a more complex and reasonable compound risk model is also obtained, where individual claim sizes are specialized to be extended negatively dependent and accident inter-arrival times are still widely lower orthant dependent, and both the claim sizes and the claim number have dominatedly varying tails.
基金supported by the National Key R&D Program of China(No.2023YFA1507902)the Science and Technology Bureau of Dalian City(No.2021RT04)+3 种基金the Shaanxi Provincial Science and Technology Department(Nos.2024JC-YBQN-0100 and QCYRCXM-2023-079)the Youth innovation team project of Shaanxi Province Education Department(No.23JP199)the Science and Technology Plan Project of Yulin Government(No.2023-CXY-137)the Initial Scientific Research Fund of High Level Talents in Yulin University(No.2023GK44).
文摘Green and atom-economic depolymerization of lignin remains a great challenge due toits complex non-repetitive structure and the inert property for chemo-digestion. A redoxneutrallignin depolymerization system without the use of extra oxidant and/or reductantover a Co-NC catalyst has been developed in this work, providing the first non-noble metalheterogeneous catalytic system for redox-neutral valorization of lignin. Mechanistic studiesbased on control reactions and deuterium labeling experiments suggest that the reactionproceeds via ametal-catalyzed dehydrogenation of C_(α)-OH to afford a carbonyl intermediate,followed by C_(β)-O bond cleavage (via hydrogenolysis) to afford monophenols and aromaticketone products. The hydrogen used for the cleavage of the C_(β)-O bond originates from thealcoholmoiety in the substrate, and the cascade dehydrogenation and hydrogenolysis stepsare highly coupled, rendering it an efficient and atom-economic process.
基金supported by the National Key R&D Program of China(No.2023YFA1507902)the National Natural Science Foundation of China(Nos.21721004 and 21878288)+1 种基金the science and technology bureau of Dalian city(No.2021RT04)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB17020100).
文摘N-participated lignin depolymerization is of great importance for the transformation of waste lignin into value-added chemicals.The vast majority of developed strategies employ organic amines as nitrogen source,and considerablemethods rely on excessive use of strong base,which suffers severe environmental issues.Herein,benzonitrile derivatives are synthesized from oxidized ligninβ-O-4 model compounds in the presence of solid nitrogen source(NH_(4))_(2)CO_(3)under mild,base-free conditions over commercially available copper catalyst.Mechanism studies suggest the transformation undergoes a one-pot,highly coupled cascade reaction path involving oxidative C-C bond cleavage and in-situ formation of C≡N bond.Of which,Cu(OAc)2 catalyzes the transfer of hydrogen from C_(β)(C_(β)-H)to C_(α),leading to the cleavage of C_(α)-C_(β)bonds to offer benzaldehyde derivative,this intermediate then reacts in-situ with(NH_(4))_(2)CO_(3)to afford the targeted aromatic nitrile product.Tetrabutylammonium iodide(TBAI),acting as a promoter,plays a key role in breaking the C_(α)-C_(β)bonds to form the intermediate benzaldehyde derivative.With this protocol,the feasibility of the production of value-added syringonitrile from birchwood lignin has been demonstrated.This transformation provides a sustainable approach to benzonitrile chemicals from renewable source of lignin.
基金Project supported by the National Natural Science Foundation of China(22221001,22131007,22102193)the National Key R&D Program of China(2021YFA1501101,2022YFA1504601)+1 种基金the 111 Project(B20027)a Startup Program of the State Key Laboratory for Oxo Synthesis and Selective Oxidation of LICP(EOSX0184)。
文摘Heterogeneous precious metal catalysts are prone to agglomeration during preparation,requiring high usage with consequently high costs.Maximizing the efficiency of precious-metal utilization is of great significance in the design of supported precious metal catalysts.Herein,2,2'-bipyridyl-5,5'-dicarboxylic acid was used as the ligand in constructing the UiO-67-Ce-BPyDC framework with Ce^(4+)coordination.This framework enables precise adsorption and coordination of Pd2+at the nitrogen sites of pyridine,promoting high dispersion of the Pd species at a single site,thereby facilitating controlled palladium loading.This precursor was used to fabricate supported Pd-based catalysts on CeO_(2)(Pd-N/CeO_(2)-P)via pyrolysis.Notably,because the Pd species are homogeneously distributed on CeO_(2)with strong interactions,Pd-N/CeO_(2)-P exhibits remarkable efficiency in cleaving the C-O bonds of diphenyl ether(DPE)to produce cyclohexanol,with a selectivity of 72.1%.The origin of the high selectivity of cyclohexanol is further elucidated using theoretical calculations;that is,DPE undergoes not only hydrogenolysis on Pd-N/CeO_(2)-P,but also hydrolysis to produce more cyclohexanol.This study not only demonstrates a successful strategy for designing highly dispersed metal catalysts,but also underscores the importance of such tailored catalysts in the advancement of sustainable lignin depolymerization technologies.
基金supported by the NSFC(11171101)Doctoral Fund of Education Ministry of China(20104306110001)the Graduate Research and Innovation Fund of Hunan Province(CX2011B197)
文摘In this paper, a compound binomial model with a constant dividend barrier and random income is considered. Two types of individual claims, main claims and by-claims, are defined, where every by-claim is induced by the main claim and may be delayed for one time period with a certain probability. The premium income is assumed to another binomial process to capture the uncertainty of the customer＇s arrivals and payments. A system of difference equations with certain boundary conditions for the expected present value of total dividend payments prior to ruin is derived and solved. Explicit results are obtained when the claim sizes are Kn distributed or the claim size distributions have finite support. Numerical results are also provided to illustrate the impact of the delay of by-claims on the expected present value of dividends.
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.
文摘The reaction characteristics of phenolic hydroxyl group were studied under the conditions of direct coal liquefaction. 2-naphthol was used as a coal model compound in this study. Under the conditions of with and without catalysts, a series of experiments were conducted at different temperatures, pressures and reaction time. Gas chromatography-mass spectrometry and gas chromatography were used to identify and quantify the reactants and products respectively. The conversion of 2-naphthol rises with the increase of reaction temperature, initial pressure and catalyst amount. The results indicated that tem- perature had a significant effect on 2-naphthol conversion, which promoted the dehydroxylation reaction. However, initial pressure had an important influence on the hydrogenation of 2-naphthol and naphthalene. The iron catalyst plays a significant role of cracking instead of hydrogenation. It is concluded that the harsh reaction conditions of high temperature, high pressure, and more catalyst are conducive to promoting dehydroxylation of 2-naphthol. The reaction mechanism was put forward based the experimental results, in which 2-tetralone was an intermediate.
基金This work is supported by the National Natural Science Foundation of China[grant number 41771484].
文摘Building façades can feature different patterns depending on the architectural style,function-ality,and size of the buildings;therefore,reconstructing these façades can be complicated.In particular,when semantic façades are reconstructed from point cloud data,uneven point density and noise make it difficult to accurately determine the façade structure.When inves-tigating façade layouts,Gestalt principles can be applied to cluster visually similar floors and façade elements,allowing for a more intuitive interpretation of façade structures.We propose a novel model for describing façade structures,namely the layout graph model,which involves a compound graph with two structure levels.In the proposed model,similar façade elements such as windows are first grouped into clusters.A down-layout graph is then formed using this cluster as a node and by combining intra-and inter-cluster spacings as the edges.Second,a top-layout graph is formed by clustering similar floors.By extracting relevant parameters from this model,we transform semantic façade reconstruction to an optimization strategy using simulated annealing coupled with Gibbs sampling.Multiple façade point cloud data with different features were selected from three datasets to verify the effectiveness of this method.The experimental results show that the proposed method achieves an average accuracy of 86.35%.Owing to its flexibility,the proposed layout graph model can deal with different types of façades and qualities of point cloud data,enabling a more robust and accurate reconstruc-tion of façade models.
基金supported by the Nature Science Foundation of Hebei Province(A2014202202)supported by the Nature Science Foundation of China(11471218)
文摘This article deals with the problem of minimizing ruin probability under optimal control for the continuous-time compound binomial model with investment. The jump mechanism in our article is different from that of Liu et al [4]. Comparing with [4], the introduction of the investment, and hence, the additional Brownian motion term, makes the problem technically challenging. To overcome this technical difficulty, the theory of change of measure is used and an exponential martingale is obtained by virtue of the extended generator. The ruin probability is minimized through maximizing adjustment coefficient in the sense of Lundberg bounds. At the same time, the optimal investment strategy is obtained.
