CHEMICAL ENGINEERING JOURNAL
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2024
·
IF 13.3
Feng Chen,Xuebin Lin,Wei Chen,Na Wen,Yanqiao Jin
The design of a highly active Cu-Co catalyst for catalytic transfer hydrogenolysis of lignin without the use of external hydrogen remains highly challenging. In this work, Cu 2 O was initially encapsulated in ZIF-67, and subsequently Cu 2 O@ZIF-67 was utilized as a precursor and sacrificial template to prepare the unique double core–shell hollow nanocage CuO@Co 3 O 4 . Co and Cu, serving as Lewis acid sites and dehydrogenation sites for the hydrogen-donor solvent isopropanol, respectively, exhibited synergistic enhancement, further increasing the catalytic activity. Under the optimal conditions of 220 °C, 1 MPa N 2 , and 4 h, the catalyst achieved 100 % conversion of 2-phenoxy-1-phenylethanol and 100 % yield towards cyclohexanol and ethylbenzene. Furthermore, the catalyst remained stable and reusable after 5 cycles, providing a practicable guidance for the value-added conversion of lignin.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
Cell Reports Physical Science
·
2024
·
IF 7.9
Qiang Wang,Ling-Ping Xiao,Qian Xu,Heng Zhang,Changzhi Li,Run-Cang Sun
Reductive catalytic fractionation of lignocellulose is a promising biorefinery strategy that combines biomass fractionation with lignin depolymerization. Herein, we report a layered copper silicate nanotube (RCuSNT) catalyst, which exhibits enhanced performance toward reductive fractionation of lignocellulose. The phenolic monomers obtained from lignin are close to the theoretical maximum yields (22.5 wt% for softwoods and 38.5 wt% for hardwoods), with high selectivity for propyl and propanol end-chain phenolic compounds. The result indicates that lignin is successfully deconstructed while cellulose and hemicellulose are retained essentially intact (88.4 wt%). The catalyst shows stability in recovery experiments, which is attributed to the immobilization of copper species by the leaf silicate. Moreover, a series of lignin model compounds and isotope-labeled reactions clarify the mechanism of C–O bond scission over RCuSNTs. This work provides a significant benchmark for the rational development of inexpensive metal catalysts in reductive catalytic fractionation systems for lignin valorization.
研究领域:
生物化学
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
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2020
·
IF 7.888
Jie Zhang,Chuang Li,Weixiang Guan,Xiaozhen Chen,Xiao Chen,Chi-Wing Tsang,Changhai Liang
Co(Ni)/MoO 3 catalysts were prepared, characterized and evaluated for the hydrogenolysis of bio-derived dibenzofuran (DBF), aiming at the understanding of the promoting effect of Co/Ni on MoO 3 for high-yield production of aromatic products. All Co(Ni)/MoO 3 catalysts selectively cleaved C-O bond, thus effectively transformed DBF to biphenyl (BP) at relatively moderate conditions. The experimental results from varying Mo species by adjusting the reduction temperature of MoO 3 together with XPS and in-situ XRD characteristic were evident that Mo 5+ species was responsible as the major active specie for the reaction. Promotional effect between Co(Ni) and Mo in Co(Ni)/MoO 3 catalysts was observed, resulted from the presence of acidic Co(Ni)MoO 4 species and a large number of Mo 5+ species both of which were created local to the Co(Ni)-O-Mo interface, as can be characterized by in-situ XRD, XPS, H 2 -TPR, NH 3 -TPD, in-situ FT-IR, Raman and TEM. The trend of the initial reaction rate follows: MoO 3 (0.18 μmol∙g cat −1 ∙s −1 ) < Ni/MoO 3 (0.26 μmol∙g cat −1 ∙s −1 ) < Co/MoO 3 (0.29 μmol∙g cat −1 ∙s −1 ), corresponding to the decreasing activation barrier. And the best catalytic activity was observed for the 100% yield of BP over Co/MoO 3 . A possible mechanism, including Co(Ni) facilitated reduction of Mo 6+ to Mo 5+ and Co(Ni) enhanced formation of acidic sites, is proposed to be responsible for the high activity in Co(Ni)/MoO 3 catalysts.
研究领域:
催化化学
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可再生能源
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材料科学
✓ 已验证
DOI
高影响因子
Science Advances
·
2020
·Vol. 6
·期 45
·
IF 13.117
Jiang Yan,Qinglei Meng,Xiaojun Shen,Bingfeng Chen,Yang Sun,Junfeng Xiang,Huizhen Liu,Buxing Han
Phenol is an important commodity chemical in the industry, which is currently produced using fossil feedstocks. Here, we report a strategy to produce phenol from lignin by directly deconstructing C sp2 –C sp3 and C–O bonds under mild conditions. It was found that zeolite catalyst could efficiently catalyze both the direct C sp2 –C sp3 bond breakage to remove propyl structure and aliphatic β carbon–oxygen (C β– O) bond hydrolysis to form OH group on the aromatic ring. The yield of phenol could reach 10.9 weight % with a selectivity of 91.8%. In this unique route, water was the only reactant besides lignin. A scale-up experiment showed that 4.1 g of pure phenol could be obtained from 50.0 g of lignin. The reaction pathway was proposed by a combination of control experiments and density functional theory studies. This work opens the way for producing phenol from lignin by direct transformation of C sp2 –C sp3 and C–O bonds in lignin.
研究领域:
催化
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绿色化学
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生物质转化
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化学工程
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有机化学
✓ 已验证
DOI
高影响因子
GREEN CHEMISTRY
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2024
·
IF 9.3
Qi Zhu,Bo Gong,Shuquan Huang,Yangxin Jin,Shengqin Liu,Shan Shao,Yuwei Yang,Taren Cataldo,Nicholas M. Bedford,Jason Chun-Ho Lam
The electrochemical selective oxidative transformation of lignin feedstocks into valuable oxygenated aromatics is essential to establish a sustainable biorefinery. In this study, we used a rhombohedral ZnIn2S4 (R-ZIS) electrocatalyst to realise the efficient anodic cleavage of C–O bonds in benzyl phenyl ether (BPE), an α-O-4 lignin model compound, to a series of industrially relevant oxygenated mono-aromatics. The reaction occurred at +2 VAg/AgCl, 65 °C, and atmospheric pressure. In optimised conditions, the reaction achieved over 99% conversion rate with a Faraday efficiency of 51.6% at 91.3% conversion of BPE, that is greater than most known electrocatalytic oxidative cleavage examples. The ZnIn2S4 electrocatalyst was deposited on a carbon cloth support, and its structural properties and surface morphology were extensively investigated. Systematic potential controlled electrolysis coupled with 18O isotopic labelling confirmed that C–O scission occurred exclusively between the benzylic carbon and phenolic oxygen. Furthermore, substrate competition studies were conducted to compare the electrocatalytic performance of the R-ZIS catalyst with that of its structural analogue, hexagonal ZnIn2S4, in terms of BPE and mono-aromatics conversion. The experimental results were supported by density functional theory calculations. The substrate scoping study revealed the suitability of the R-ZIS induced electrocatalytic system for a variety of substituted α-O-4/β-O-4 model dimers. Overall, this work demonstrates an efficient anodic process that can enable the atom-efficient valorisation of lignin to produce oxygenated aromatics. The proposed approach can complement the numerous existing reductive lignin cleavage methods.
研究领域:
化学工程
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可再生资源利用
·
电化学催化
✓ 已验证
产品关联
DOI
高影响因子
BMC Chemistry
·
2019
·Vol. 13
·期 1
·1-15
·
IF 0
Guo J.,Ma Yu L.,Yu Jia Y.,Gao Yu J.,Ma Ning X.,Wu Xiao Y.
Herein, 2-(2-methoxyphenoxy)-1-phenylethanol (β- O -4), 2-methoxyphenyl anisole (α- O -4) and 4-phenoxyphenol (4- O -5) were selected as typical lignin model compounds. Given the effectiveness of traditional acid–base catalysts for lignin depolymerisation, a novel Ni/CaO–H-ZSM-5(60) catalyst was prepared to investigate the difficulty level of C–O bond of three model compounds cleavage in ethanol. It was observed that Ni/CaO–H-ZSM-5(60) had prominent performance on the C–O bond cleavage at very mild conditions (140 °C, 1 MPa H 2 ). Among them, the C–O bond of α- O -4 and β- O -4 could be completely cleaved within 60 min. Although the C–O bond of 4- O -5 had high bond energy, 41.2% of conversion was occurred in 60 min. The introduction of CaO could regulate the acidity of H-ZSM-5 to enhance the ability to break C–O bonds. Moreover, the possible pathways of C–O ether bonds in three lignin model compounds cleavage were proposed in order to selectively obtain target products from the raw lignin degradation.
研究领域:
化学工程
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催化科学
✓ 已验证
DOI
JOURNAL OF CATALYSIS
·
2020
·
IF 7.888
Yanru Zhu,Jian Zhang,Xiaodan Ma,Zhe An,Shaowei Guo,Xin Shu,Hongyan Song,Xu Xiang,Jing He
Complexity of chemical linkages (C-C/C-H/C-O, C=C/C=O, or C-O-H/C-O-C) in biomass-derived molecules makes the selective activation of targeted bonds much more challenging, expecting well-defined catalysts and definite catalytically-active sites. This work demonstrates an effective gradient reduction strategy to control the definite structure of catalytically-active sites, affording defects-rich nano-twin Cu particles. This strategy just involves the reduction (calcination under H 2 ) of Cu II -containing layered double hydroxides (LDHs) simply with controlling the reduction gradient (interval time) of Cu II species in two chemical micro-environments (Cu II -O-Cu II and Cu II -O-M II/III/IV (M ≠ Cu)) in the brucite-like layer of LDHs. The nano-twin Cu particles efficiently promote the target activation of C-O and C=C in the conversion of furfural to cyclopentanone (CPO). With ~100% furfural conversion, the defects-rich nano-twin Cu particles afford a CPO selectivity of 92%, 50% higher than regular spherical Cu particles. The multi-stepped defect sites, originating from the planar defects, play a decisive role in promoting the CPO selectivity by facilitating the hydro-deoxygenation to C-O of 4-hydroxycyclopentenone (HCP) and hydrogenation to C=C of HCP or cyclopentenone.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2024
·
IF 3.8
Hongyu Qu,Xiangcheng Li,Xiao Han,Junjie Li,Xinqiang Feng,Chuang Liu,Zhendong Wang,Weimin Yang
Rational design of highly efficient non-noble-metal catalysts for the selective hydrogenolysis of biomass platform compounds to produce fuels and fine chemicals is a key pursuit for the sustainable chemical industry. In this work, we report for the first time the synthesis of a Ni-supported germanosilicate zeolite (Ni-SCM-14) catalyst by a simple grinding method, showing both satisfactory yield (90.3%) and good stability in eight cycles for the hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF). Characterization revealed that Ni nanoparticles were highly dispersed on the SCM-14 zeolite with strong interactions. The synergistic effect of highly dispersed Ni hydrogenation sites and the weak acidity activation of the C–O bond provided by SCM-14 is considered to be the key to the efficient hydrogenolysis of HMF. This discovery opens up a new avenue for germanosilicate zeolite to activate the C–O bond.
研究领域:
催化化学
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生物质转化
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
AICHE JOURNAL
·
2025
·
IF 4
Jinlin Mei,Zhentao Liu,Zhengkai Cao,Aocheng Wang,Xiaoyang Kong,Aijun Duan,Chunya Wang,Chunming Xu,Xilong Wang
Hierarchical Y/SBA-15 meso-microporous composites (YS- x ) and corresponding highly dispersed catalysts (Ni/YS- x ) were prepared and applied to the production of jet fuel range hydrocarbons by the selective hydrogenation of oleic acid. Small particle size and electron-deficient Ni δ+ are detrimental to the C C bond activation of the η 1 (C)-acyl conformation and inhibit the decarbonylation/decarboxylation pathway. Besides, the activation ability of the C C bond is regulated to avoid excessive cleavage by the acidity and diffusion properties of the hierarchical Ni/YS- x catalysts, thus affecting their hydroisomerization and hydrocracking properties. The abundant acid sites are beneficial to the selective activation of the C O bond of the η 2 (C, O)-aldehyde conformation and the promotion of the reductive deoxygenation pathway. The optimal Ni/YS-1 shows the highest iso / n -alkane ratio ( i / n = 6.26) and superior jet fuel range hydrocarbons yield (48.8%, 340°C), which is a benefit from its outstanding acid–metal balance and worthy diffusion property.
研究领域:
催化
·
多孔材料
·
化学反应工程
·
能量转换
·
表面化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Lin Ai,Yanping Chen,Fang Lu,Jiaxu Liu,Xiao-Feng Wu,Shengjun Huang
The fundamental challenge in the gas-phase selective hydrogenation of α,β-unsaturated aldehydes to α,β-unsaturated alcohols lies in the construction of microscopic environment for the preferential hydrogenation of C = O bond along with the preservation of C = C bond under the reductive atmosphere. Herein, we proposed a structure-matching strategy for the catalyst design, in which In component in metallic form and oxide form are interplayed with metallic Ni and Al 2 O 3 support, respectively. The fabrication of In-Ni intermetallic compound stokes up the desirable electropositive-electronegative environment (In δ+ -Ni δ- ) for the adsorption of polar carbonyl group. The In species in the In-oxo form are engaged in the network of Al 2 O 3 support in the formation of In-O-Al-O entities, which stabilizes the heterolytically dissociated H species to match the preferential saturation of polar C = O bond. Therefore, the resulting In-Ni-Al 2 O 3 catalyst achieves a selectivity of 77.2 % to methallyl alcohol with a conversion of 53.8 % in the gas-phase hydrogenation process, which present a striking contrast to the outcomes upon the counterpart Ni-Al 2 O 3 (non-selectivity to methallyl alcohol). Such structure-matching strategy enriches the fundamental understandings and basis for the rational design of catalysts for the selective hydrogenation of unsaturated aldehydes.
研究领域:
催化
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化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
iScience
·
2023
·
IF 5.8
Chengcheng Suo,Wei Li,Sha Luo,Chunhui Ma,Shouxin Liu
Summary Photocatalytic depolymerization is a high value-added approach for utilization of lignin. In this study, magnetic microspheres of FeCoRu@SiO 2 –TiO 2 were synthesized by a co-precipitation method. Doping with CoO x and RuO x was used to improve the response to visible light, and doping with TiO 2 was used to improve the response to ultraviolet light ( λ < 380 nm). The lignin model compound depolymerization rate was >90%. The electron paramagnetic resonance results showed that the reaction occurred in two steps (aerobic phase and oxygen-free phase). Most of the O 2 − was produced in the first step by cleavage of C-O bonds. The second step was inhibited in an oxygen-free atmosphere. This research provides a valid method for enhancing the photocatalytic properties using full-spectrum light and exploring the lignin photocatalytic depolymerization mechanism. Further research is required to develop the catalyst properties and performance to produce radicals.
研究领域:
化学
·
材料科学
·
环境科学
·
催化
✓ 已验证
DOI
高影响因子
ChemSusChem
·
2025
·
IF 6.6
Zixuan Tan,Yihong Cai,Bo Yang,Hao Huang,Haijun Guo,Min Zhuang,Hui Luo,Qingwei Meng,Shaoqu Xie
Graphical Monohydric alcohols are a potential fuel, and herein, monohydric alcohols have been selectively synthesized from multicarbon sugars by modulating the electron distribution of Ru and enhancing the hydrodeoxygenation process of biomass. Ru-based catalysts are widely used in catalytic reactions, but the electron-deficient nature promotes strong decarbonylation, leading to complete deoxygenation during the conversion of polyhydroxy biomass. Despite extensive research, effectively suppressing this decarbonylation activity remains challenging. Herein, electron-rich Ru and electron-deficient Ni formed due to the electron migration of Ni → Ru have a synergistic catalytic effect, controlling the precise cleavage of C N bonds by Ru 0 and retaining most of the C O bonds. The amorphous Al 2 O 3 is sufficiently bound to the substrate to promote rapid hydrogenation. This modification effectively suppresses the intrinsic decarbonylation activity of Ru and improves selectivity for hydrodeoxygenation. Using carbohydrates as substrates, the Ru–Ni bimetallic catalysts preferentially promote the hydrodeoxygenation pathway, resulting in a significant increase in C3+ monohydric alcohol yields. This work presents a new strategy for modulating reaction pathways via electronic structure engineering, offering valuable insights into the potential of Ru–Ni systems for biomass conversion and sustainable alcohol synthesis.
研究领域:
催化化学
·
材料科学
·
化学工程
·
生物质转化
·
可持续化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）