BIOMASS & BIOENERGY
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2026
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IF 7
Yahui Zhang,Haowen Cui,Haian Xia
The selective oxidation of furfural (FF) to 2-furoic acid (FA) represents a significant route toward sustainable chemical production. However, existing catalytic systems often suffer from limitations such as low substrate concentrations, harsh reaction conditions, and inadequate selectivity. In this study, a series of Ag/ZrO 2 catalysts with varying Ag loadings were prepared via a deposition–precipitation method and were used for the aerobic oxidation of FF to FA under mild conditions. The effects of metal loading, catalyst mass, reaction temperature, reaction time, and oxygen pressure on FF conversion and FA selectivity were systematically investigated. Under optimized conditions, nearly 100% FA was achieved under 10 wt% FF concentration at low-temperature (ca. 5 °C), while a high selectivity of 90.3% toward FA was maintained even at 20 wt% FF. The catalysts also exhibited excellent recyclability, retaining over 85% FA selectivity after five consecutive cycles. Comprehensive characterization techniques, including XRD, XPS, and HRTEM, were employed to elucidate the structure-activity relationship of the catalysts. The experimental and characterization findings propose a possible reaction mechanism involving synergistic effects of Ag 0 sites for dehydrogenation and ZrO 2 oxygen vacancies for O 2 activation. This work represents a notable advance in the field, as it develops the high efficient catalytic system under high FF concentrations and low-temperature conditions for the first time.
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BIORESOURCE TECHNOLOGY
·
2026
·
IF 8.2
Chen-Xi Li,Qian Ren,Feng Peng,Ming-Fei Li
A synergistic catalyst was prepared on lignin-derived carbon via two-step strategy. • The catalyst achieved an exceptional lactic acid yield of 58.91% from xylan. • The catalyst demonstrated remarkable versatility across diverse biomass-derived sugars. • High recyclability was realized attributable to Co–N 4 /Zn AC configuration. Hydrothermal catalysis offers a sustainable route for lignocellulosic valorization, while conventional catalysts often necessitate demanding conditions and efficient hemicellulose conversion remains challenging. Herein, a nitrogen-doped lignin-derived carbon-based synergistic catalyst, embedding cobalt single-atom and zinc atomic clusters (Co SAC -Zn AC @LCN), was constructed via a pre-coordination and pyrolysis two-step coupled strategy for one-pot conversion of hemicellulose to lactic acid (LaA). Characterizations revealed well-dispersed and spatially proximate Co single-atom and Zn clusters anchored on stacked two-dimensional carbon–nitrogen nanosheets. The strong synergistic interaction between Co single-atom and Zn clusters enhanced Lewis acidity and further facilitated C C bond cleavage and intermediate rearrangement. Co SAC -Zn AC @LCN exhibited a mesoporous structure with a high surface area (140.61 m 2 /g) and elevated carbon defects, promoting reactant diffusion and adsorption. Under optimized conditions (240 °C, 1 h), the catalyst achieved 58.9% LaA yield and 113.7 h −1 TOF from xylan and maintained over 42% yield across various biomass-derived sugars, demonstrating its remarkable catalytic performance and universality. Owing to the stable Co–N 4 /Zn AC configuration, it retained over 56% LaA yield after six cycles. This work provides a general strategy to design atomic-scale synergistic catalysts from biomass carbon for efficient lignocellulosic conversion to high-value chemicals. A nitrogen-doped carbon catalyst embedded with Co single-atom and Zn atomic clusters was constructed leveraging a lignin-derived framework. The strong synergistic interaction between Co single-atom and Zn clusters enhanced Lewis acidity and facilitated the efficiently conversion of hemicellulose to lactic acid. Owing to the stable Co–N 4 /Zn AC configuration, it retains excellent cycling stability. Download: Download high-res image (145KB) Download: Download full-size image
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INORGANIC CHEMISTRY
·
2025
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IF 4.7
Hui Hu,Honghui Xie,Sanqi Liang,Mengting Yu,Fanglin Liu,Shengjun Deng,Shuhua Wang,Weiming Xiao,Chao Chen
The reports on MOFs supported nonprecious metal nanocatalysts (NPM/MOFs) remain limited, primarily due to the conflict between the harsh conditions for the preparation of nonprecious metal nanoparticles and the poor stability of MOFs; the fabrication of NPM/MOFs has long been a challenge. Herein, we demonstrate a facile, versatile, and sustainable method to fabricate NPM/MOFs by directly reacting commercial metal dusts with the ligands through simple ball milling. In this approach, the metal dusts were sacrificed in situ to form the corresponding MOFs and etched into smaller nanoparticles at the same time. The developed approach entirely circumvents the harsh conditions typically required for the preparation of nonprecious metal nanoparticles, while preserving the porous structures of the MOFs. By this facile approach, several NPM/MOFs with intact pore structures were prepared. Moreover, this approach consumes trace amounts of solvent, conforming to the concept of sustainable synthesis. In addition, the synthesized Co/ZIF-67 nanocatalyst was tested in the hydrogenation of unsaturated aldehydes; it exhibits an exceptionally catalytic performance that is comparable to many noble metal nanocatalysts.
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POLYMER DEGRADATION AND STABILITY
·
2025
·
IF 7.4
Gang Tang,Feilong Wang,Wei Yang,Cunlong Fu,Zicheng Xu,Xiuyu Liu,Xiaoyan Du,Xin Wang
Currently, most commercial epoxy thermosets are derived from the thermal curing of diglycidyl ether of bisphenol A (DGEBA)-type epoxy prepolymers, whose manufacture is highly dependent upon fossil resources. Over the past decade, increasing efforts have been devoted to developing bio-based epoxy monomers to replace DGEBA-type epoxy prepolymers for sustainable development. Another shortcoming of DGEBA-type epoxy thermosets is their high fire risk. To overcome the above issues, a bio-based epoxy monomer, N, N-diglycidyl furfurylamine (DGFA), was synthesized from furfurylamine, and a bio-based flame retardant (DFDA-DPPO) was also synthesized from furfurylamine, furfural, and diphenylphosphine oxide (DPPO). DFDA-DPPO was incorporated into DGFA at different loadings to prepare a series of flame-retardant bio-based epoxy thermosets, with 4, 4’-diaminodiphenylmethane (DDM) as a hardener. The influence of DFDA-DPPO on the curing kinetics, thermal stability, mechanical strength and flame-retardant properties of DGFA/DDM thermosets was investigated. Specifically, the DGFA/DDM thermoset with a 1.5 % phosphorus content achieved a tensile strength of 81.9 MPa, an impact strength of 16.7 kJ/m 2 , an LOI of 33.5 %, a UL94 V-0 rating, and a glass transition temperature of 98.5 °C. Furthermore, the flame-retardant mechanisms of DFDA-DPPO were also studied in both the condensed and gaseous phases. This work provides a good substitute for DGEBA in the fabrication of bio-based epoxy thermosets with combined mechanical properties, thermal stability and flame retardancy.
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BIORESOURCE TECHNOLOGY
·
2023
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IF 11.4
Meixin Wang,Yawei Zhan,Jiayue Zhao,Zhiqiang Li
Bamboo and its mechanical processing residues have broad prospects for high value-added utilization. In this research, p-toluenesulfonic acid was used for the pretreatment of bamboo to investigate the effects of extraction and depolymerization of hemicellulose. The response and behavior of changes of cell-wall chemical components were investigated after different solvent concentration, time, and temperature pretreatment. Results indicated that the maximum extraction yield of hemicellulose was 95.16 % with 5 % p-toluenesulfonic acid at 140 °C for 30 min. The depolymerized components of hemicellulose in the filtrate were mainly xylose and xylooligosaccharide, with xylobiose accounting for 30.77 %. The extraction of xylose from the filtrate reached a maximum of 90.16 % with 5 % p-toluenesulfonic acid at 150 °C for 30 min pretreatment. This research provided a potential strategy for the industrial production of xylose and xylooligosaccharide from bamboo and for the future conversion and utilization.
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Fermentation-Basel
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2023
·Vol. 9
·期 3
·286
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IF 3.7
Hongsen Zhang,Jiahui Jiang,Conghui Quan,Guizhong Zhao,Guotao Mao,Hui Xie,Fengqin Wang,Zhimin Wang,Jian Zhang,Pingping Zhou,Andong Song
Inhibitors from lignocellulosic biomass have become the bottleneck of biorefinery development.Gluconobacter oxydansDSM2003 showed a high performance of inhibitors degradation, which had a short lag time in non-detoxified corn stover hydrolysate and could convert 90% of aldehyde inhibitors to weaker toxic acids. In this study, an aldehyde dehydrogenase geneW826-RS0111485, which plays an important function in the conversion of aldehyde inhibitors inGluconobacter oxydansDSM2003, was identified.W826-RS0111485was found by protein profiling, then a series of enzymatic properties were determined and were heterologously expressed inE. coli. The results indicated that NADP is the most suitable cofactor of the enzyme when aldehyde inhibitor is the substrate, and it had the highest oxidation activity to furfural among several aldehyde inhibitors. Under the optimal reaction conditions (50 °C, pH 7.5), theKmandVmaxof the enzyme under furfural stress were 2.45 and 80.97, respectively, and theKcatwas 232.22 min−1. The biodetoxification performance experiments showed that the recombinantE. colicontaining the target gene completely converted 1 g/L furfural to furoic acid within 8 h, while the controlE. colionly converted 18% furfural within 8 h. It was further demonstrated thatW826-RS0111485played an important role in the detoxification of furfural. The mining of this inhibitor degradation gene could provide a theoretical basis for rational modification of industrial strains to enhance its capacity of inhibitor degradation in the future.Keywords:inhibitors degradation;Gluconobacter oxydans;protein profiling;aldehyde dehydrogenase;furfural
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Nature Communications
·
2023
·Vol. 14
·期 1
·1-11
·
IF 16.6
Chen Zhe,Li Jili,Meng Lingshen,Li Jianan,Hao Yaming,Jiang Tao,Yang Xuejing,Li Yefei,Liu Zhi-Pan,Gong Ming
Simultaneously achieving abundant and well-defined active sites with high selectivity has been one of the ultimate goals for heterogeneous catalysis. Herein, we construct a class of Ni hydroxychloride-based inorganic-organic hybrid electrocatalysts with the inorganic Ni hydroxychloride chains pillared by the bidentate N-N ligands. The precise evacuation of N-N ligands under ultrahigh-vacuum forms ligand vacancies while partially retaining some ligands as structural pillars. The high density of ligand vacancies forms the active vacancy channel with abundant and highly-accessible undercoordinated Ni sites, exhibiting 5-25 fold and 20-400 fold activity enhancement compared to the hybrid pre-catalyst and standard β-Ni(OH) 2 for the electrochemical oxidation of 25 different organic substrates, respectively. The tunable N-N ligand can also tailor the sizes of the vacancy channels to significantly impact the substrate configuration leading to unprecedented substrate-dependent reactivities on hydroxide/oxide catalysts. This approach bridges heterogenous and homogeneous catalysis for creating efficient and functional catalysis with enzyme-like properties.
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INDUSTRIAL CROPS AND PRODUCTS
·
2023
·
IF 5.9
Na Li,Huan Xia,Shiyuan Liu,Junjiang Teng,Yanbin Jiang
In order to improve the activity and reusability of β-xylosidase, the β-xylosidase mutant S160N-R333H (R333H) which could convert notoginsenoside R1 to ginsenoside Rg1 and xylose was immobilized on the metal-organic framework (MOF) UiO-66-NH 2 . The physical and biochemical properties of immobilized β-xylosidase ( [email protected] 2 ) were studied in detail. The results showed improved performances, i.e. the high immobilization yield of 93% and recovery activity of 192.8%, better stability under acidic or trypsin-containing conditions, the higher activity in the reaction containing ions , and the improved catalytic efficiency (was 1.37-fold than that of free R333H). Importantly, the ginsenoside Rg1 yields remained more than 80% after six recycles in McIlvaine buffer and pure water. The UiO-66-NH 2 could catalyze xylose dehydration to produce furfural and the yield reached 69%. Thus this study provides a promising method for production of bioactive or platform chemicals via continuous conversion of xyloylated substrates using nanocatalyst synthesized by β-xylosidase and MOF.
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POLYMER DEGRADATION AND STABILITY
·
2023
·
IF 5.9
Yadong Wang,Li Ma,Jun Yuan,Zongmin Zhu,Xiaoming Liu,Dengsong Li,Liqing He,Fei Xiao
The development of high-performance EP composites with high glass transition temperature (T g ), excellent flame retardancy, and UV resistance is a challenging topic in the flame retardancy community. In this work, a bio-based phosphorus/nitrogen/sulfur (P/N/S) containing flame retardant (FDI) was prepared from furfural, 2-amino-5-nitrothiazole, and DOPO. It was applied to improve the flame retardant, dielectric, and UV-resistant properties of EP. Thanks to the combination of phosphorus, nitrogen, and sulfur in FDI, the EP/FDI composites showed superior flame retardancy. Only adding 5 wt% FDI made EP achieve UL-94 V-0 flammability rating with a limiting oxygen index (LOI) of 27%. Meanwhile, EP/FDI-5% composite showed significant reduction of 65.1% and 33.6% in total smoke production (TSP) and the peak heat release rate (pHRR), respectively. The flame-retardant mechanisms of EP/FDI thermosets were investigated by residual char photographs, SEM, XPS, and Py/GC-MS. Moreover, compared to pure EP, EP/FDI composites showed excellent UV resistance, low dielectric properties, and high glass transition temperature, which was expected to be extensively used in multiple areas of production.
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CATALYSIS LETTERS
·
2023
·
IF 2.8
Xu Lingling,Pan Xiaomei,Wu Ningxin,Gao Lijing,Xiao Guomin
The conversion of biomass energy sources is a crucial direction in the transformation of energy resources, such as cellulose to high-value chemicals. As an important platform compound, 5-hydroxymethylfurfural (HMF) is one of the worthwhile products from biomass. Previously, the use of Hf/ZSM-5 catalyst demonstrated excellent catalytic performance, with the yield of HMF reaching 67.50% under optimal reaction conditions (120 min, 190 °C, H 2 O(NaCl)/THF). Based on the previous work, the effect of a series of metal salts on the preparation of HMF from cellulose catalyzed by Hf/ZSM-5 catalyst was investigated in this paper. This result demonstrates the addition of AlCl 3 promoted the production of HMF yield and AlCl 3 completed with excellent performance among five metal salts. Moreover, the yield of HMF was improved to 70.95% by adjusting the optimal reaction conditions. Graphical Abstract
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2023
·
IF 4.2
Xingyilong Zhang,Houfang Lu,Man Zhang,Hui Han,Rubo Tian,Kejing Wu,Yingying Liu,Yingming Zhu,Bin Liang
Low-temperature production of 5-hydroxymethylfurfural (HMF) from fructose in ternary deep eutectic solvents (TerDESs) of choline chloride (ChCl), ethylene glycol (EG), and maleic acid (MalA) is proposed. A fructose conversion of 99.9% and an HMF yield of 87.3% are achieved in TerDES with ChCl/EG/MalA = 3:1:1 at 70 °C in 30 min. The ChCl can effectively activate the hydroxy groups of fructose by lengthening the C–O bonds. The EG can both improve the formation of ChCl–MalA DES with wide ranges of component ratios and reduce the viscosity of the DES. A reaction mechanism considering the synergistic effect of the components in TerDES is suggested to explain the enhanced dehydration of fructose under mild conditions. The recycling results of the TerDES show stable yields of HMF within five recycle runs. This work offers an efficient solution to a green and sustainable process for a high yield of HMF production.
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Catalysts
·
2023
·Vol. 13
·期 4
·663
·
IF 3.9
Xu Wu,Heqin Guo,Litao Jia,Yong Xiao,Bo Hou,Debao Li
The base-free oxidation of furfural by non-noble metal systems has been challenging. Although MnO2emerges as a potential catalyst application in base-free conditions, its catalytic efficiency still needs to be improved. The crystalline form of MnO2is an important factor affecting the oxidation ability of furfural. For this reason, four crystalline forms of MnO2(α, β, γ, and δ-MnO2) were selected. Their oxidation performance and surface functional groups were analyzed and compared in detail. Only δ-MnO2exhibited excellent activity, achieving 99.04% furfural conversion and 100% Propo.FA(Only furoic acid was detected by HPLC in the product) under base-free conditions, while the furfural conversion of α, β, and γ-MnO2was below 10%. Characterization by XPS, IR, O2-TPD and other means revealed that δ-MnO2has the most abundant active oxygen species and surface hydroxyl groups, which are responsible for the best performance of δ-MnO2. This work achieves the green and efficient oxidation of furfural to furoic acid over non-noble metal catalysts.Keywords:base-free;MnO2;crystal type;furfural oxidation to furoic acid
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