JOURNAL OF CATALYSIS
·
2017
·
IF 6.844
Huifang Liu,Min Wang,Hongji Li,Nengchao Luo,Shutao Xu,Feng Wang
Catalytic oxidation of C C bond is a key technology to transform petroleum-based as well as sustainable biomass feedstock into more valuable oxygenates. We herein describe a convenient and useful oxidation strategy of converting ketones into carboxylic acids using homogeneous copper catalyst without additives and with O 2 as the terminal oxidant. A wide range of aryl and aliphatic ketones as well as β–O–4 lignin models were selectively oxidized to acids via C C bond cleavage. Mechanism studies by EPR and in situ NMR elucidate the principles of Cu/O 2 reactivity that involves C H bond and O 2 activation via a peroxide species. This provides an important foundation for expanding the scope of useful aerobic oxidation reactions using copper catalysts.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Song Han,Yun Zhao,Mina Liang,Jinshui Su,Xiangxiong Zhai,Qi Zhang,Guoling Li,Zhonghai Ni
The photocatalytic cleavage of C α -C β bonds in lignin holds considerable potential for the production of value-added chemicals. Lignin consists of phenylpropane units interconnected by a variety of complex chemical bonds. Specifically, C-O bonds are more prevalent and relatively easier to cleave, whereas C–C bonds exhibit higher bond energy, rendering them more difficult to cleavage under conventional conditions. This study presents a phosphotungstic acid/phosphoric acid-functionalized porous tubular C 3 N 4 composite photocatalyst (PW/P-TCN). H 3 PO 4 modified PW/P-TCN surfaces enhance O 2 adsorption, improve separation and transfer of photogenerated carriers, and increase exposure of active sites. This promotes reactant adsorption and significantly boosts photocatalytic efficiency. Through this strategy, 1,2-diphenylethanol (DPol), used as a typical model substrate, is fully converted into aromatic monomers, achieving a DPol conversion rate of 99.9 %. Mechanistic studies reveal that C α -C β bond cleavage primarily involves the photo-oxidation mechanism mediated by electron-hole coupling. The construction of the PW/P-TCN heterojunction is essential for simultaneously sustaining robust reduction and oxidation capabilities. Natural lignin samples are applied to the photocatalytic system, and successful C–C bond cleavage depolymerization is achieved under optimal reaction conditions. This study offers valuable insights for the design of more economical and efficient photocatalysts for lignin depolymerization.
研究领域:
材料科学
·
环境科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2019
·
IF 12.221
Huifang Liu,Hongji Li,Nengchao Luo,Feng Wang
Lignin is the largest carrier of aromatics on earth, and its depolymerization can afford value-added aromatic products. Direct cleavage of the C–C bonds in lignin linkages is significant, but it is challenging to obtain low-molecular-weight aromatic monomers. Herein, using vanadium catalysts under visible light, we selectively cleave the C–C bonds in β-1 and β-O-4 interlinkages occluded in lignin models and extracts by an oxidative protocol. Visible light irradiation triggered single electron transfer between the substrate and the catalyst, which further induced the selective Cα–Cβ bond cleavage and generated the final aromatic products through radical intermediates. Using this photocatalytic chemistry, the reactivity of lignin models and the selectivity of Cα–Cβ bond cleavage were significantly improved. More importantly, this protocol affords aromatic monomers through the fragmentation of organosolv lignins even at room temperature, indicating the potential of photocatalytic C–C bond cleavage of lignin linkages under ambient conditions.
研究领域:
化学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2025
·
IF 4.9
Wei Wang,Rui Zhang,Jiaqing Li,Huai Liu,Wenlong Jia,Junhua Zhang,Dan Li,Lincai Peng
Furans are important scaffolds with applications in pharmaceuticals, polymers synthesis and biofuels. The direct production of new types of furans from glucose is therefore significant but remains a great challenge. Herein, we report a facile strategy to produce acetylfurans directly from glucose over MoCs-SiO 2 , with an increase in yield from 35.8 % to 81.4 % compared with pristine Mo-SiO 2 due to the facilitated C−C bond cleavage of glucose. The incorporation of Cs improved the dispersion of Mo species, induced the formation of partially reduced Mo, increased the Lewis acidity and glucose adsorption of the catalyst, and thus shifting the reaction selectivity from C−C coupling to cleavage. Kinetic studies further demonstrated the positive contribution of Cs as a promoter in lowering the activation energy of C−C bond cleavage. This study provides a promising strategy to broaden the range of furanic compounds derived from glucose for product-oriented biorefineries.
研究领域:
化学工程
·
生物催化
·
可再生资源利用
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Xiaotong Yang,Kaiyu Dong,Zhe Zheng,Yuehuan Zhang,Qiang Yuan
Efficient C C bond cleavage and the complete oxidation of alcohols are key to improving the efficiency of renewable energy utilization. Herein, we successfully prepare porous Fe-doped hexagonal close-packed ( hcp )-PtBi/face-centered cubic ( fcc )-Pt heterostructured nanoplates with abundant grain/phase interfaces ( h -PtBi/ f -Pt@Fe 1.7 PNPs) via a simple solvothermal method. The open porous structure, abundant grain/phase interface and stacking fault defects, and the synergistic effect between intermetallic hcp -PtBi and fcc -Pt make h -PtBi/ f -Pt@Fe 1.7 PNPs an effective electrocatalyst for the glycerol oxidation reaction (GOR) in direct glycerol fuel cells (DGFCs). Notably, the h -PtBi/ f -Pt@Fe 1.7 PNPs exhibit an excellent mass activity of 7.6 A mg Pt −1 for GOR, 4.75-fold higher than that of commercial Pt black in an alkaline medium. Moreover, the h -PtBi/ f -Pt@Fe 1.7 PNPs achieve higher power density (125.8 mW cm −2 ) than commercial Pt/C (81.8 mW cm −2 ) in a single DGFC. The h -PtBi/ f -Pt@Fe 1.7 PNPs can also effectively catalyze the electrochemical oxidation of 1-propanol (17.1 A mg Pt −1 ), 1,2-propanediol (7.2 A mg Pt −1 ), and 1,3-propanediol (5.2 A mg Pt −1 ). The in-situ Fourier-transform infrared spectra further reveal that the C C bond of glycerol, 1-propanol, 1,2-propanediol, and 1,3-propanediol was dissociated for the complete oxidation by the h -PtBi/ f -Pt@Fe 1.7 PNPs. This study provides a new class of porous Pt-based heterostructure nanoplates and insight into the intrinsic activity of different C3 alcohols.
研究领域:
材料科学
·
能源化学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nature Communications
·
2021
·Vol. 12
·期 1
·1-12
·
IF 14.919
Xie Chao,Lin Longfei,Huang Liang,Wang Zixin,Jiang Zhiwei,Zhang Zehui,Han Buxing
Selective cleavage of C-C bonds is very important in organic chemistry, but remains challenging because of their inert chemical nature. Herein, we report that Zn/NC-X catalysts, in which Zn 2+ coordinate with N species on microporous N-doped carbon (NC) and X denotes the pyrolysis temperature, can effectively catalyze aerobic oxidative cleavage of C(CO)-C bonds and quantitatively convert acetophenone to methyl benzoate with a yield of 99% at 100 °C. The Zn/NC-950 can be applied for a wide scope of acetophenone derivatives as well as more challenging alkyl ketones. Detail mechanistic investigations reveal that the catalytic performance of Zn/NC-950 can be attributed to the coordination between Zn 2+ and N species to change the electronic state of the metal, synergetic effect of the Zn single sites with their surrounding N atoms, as well as the microporous structure with the high surface area and structural defects of the NC.
研究领域:
有机化学
·
催化材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
·
2018
·Vol. 20
·期 26
·17942-17951
·
IF 3.906
Muge Niu,Yucui Hou,Weize Wu,Shuhang Ren,Ru Yang
Vanadium(V)-catalyzed aerobic oxidation in aqueous solution shows high selectivity in the field of C–C bond cleavage of carbohydrates for chemicals with less carbon atoms. However, the pathway of C–C bond cleavage from carbohydrates and the conversion mechanism are unclear. In this work, we studied the pathway and the mechanism of D-glucose oxidation to formic acid (FA) in NaVO3–H2SO4 aqueous solution using isotope-labeled glucoses as substrates. D-Glucose is first transformed to FA and D-arabinose via C1–C2 bond cleavage. D-Arabinose undergoes similar C1–C2 bond cleavage to form FA and the corresponding D-erythrose, which can be further degraded by C1–C2 bond cleavage. Dimerization and aldol condensation between carbohydrates can also proceed to make the reaction a much more complicated mixture. However, the fundamental reaction, C1–C2 bond cleavage, can drive all the intermediates to form the common product FA. Based on the detected intermediates, isotope-labelling experiments, the kinetic isotope effect study and kinetic analysis, this mechanism is proposed. D-Glucose first reacts with a vanadium(V) species to form a five-membered-ring complex. Then, electron transfer occurs and the C1–C2 bond weakens, followed by C1–C2 bond cleavage (with no C–H bond cleavage), to generate the H3COO˙–vanadium(IV) complex and D-arabinose. FA is generated from H3COO˙ that is oxidized by another vanadium(V) species. The reduced vanadium species is oxidized by O2 to regenerate to its oxidation state. This finding will provide a deeper insight into the process of C–C bond cleavage of carbohydrates for chemical synthesis and provide guidance for screening and synthesizing new highly-efficient catalyst systems for FA production.
研究领域:
化学
·
生物化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Catalysts
·
2025
·Vol. 15
·期 3
·258
·
IF 4
Ling Xie,Zilong Huang,Yapeng Zhan,Jiahao Huang,Chao Wang,Riyang Shu,Junyao Wang,Libin Lei,Jianping Liu,Zhipeng Tian,Ying Chen
Cleavage of C-C bonds is crucial for hydrogen production via aqueous phase reforming of biomass-derived oxygenates. In this study, the hydrogen production performance and C-C bond cleavage capacity of Ni-W/AC catalysts with varying W/Ni ratios are evaluated using ethylene glycol as a model compound. A series of APR experiments conducted suggests that Ni-0.2W/AC catalyst exhibits the highest C1/C2+ratio of 15.87 and achieves a hydrogen yield of 47.76%. The enhanced Ni-W bimetallic interactions, which significantly improve the efficiency of C-C bond cleavage and increase catalyst activity by promoting active site dispersion, are confirmed by detailed characterization techniques. Further analysis of product distribution provides insights into the reaction pathways of ethylene glycol and the reaction mechanism for ethanol during aqueous phase reforming. All the results indicate that this catalytic reforming method effectively facilitates C-C bond cleavage and hydrogen production, contributing to a better understanding of APR mechanisms for biomass-derived oxygenates.
研究领域:
催化化学
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Pei-dong Wu,Lanyun Li,Hu Li,Zhen Fang
Sustainable upgrading of biomass to high-value chemicals is greatly dependent on catalytic C-C/C-O bond cleavage of high selectivity. Here, an oxidation-enhanced photoelectrochemical protocol was developed to be capable of breaking different types of C-C bonds for efficiently producing aromatic carboxylic acids (85.0–99.8% yields) from lignin. Ni local electronic state of the prepared F-Fe 2 O 3 -Co:NiO x H y with excellent durability could be modulated, and high-valence Ni(Ⅳ) reactive species played a key role in the oxidative C-C bond scission of various lignin models. In-situ characterization and control experiments indicated that photocatalytic radical and electrocatalytic interface facilitated C-H/O-H delocalization, contributing significantly to the enhanced oxidation process. In addition, quantum calculations elaborated that photo-excited holes and Ni(Ⅳ) are key reactive species for enhancive electrocatalytic cleavage of different C-C bonds in lignin to exclusively furnish aromatic carboxylic acids. This research provides a renewable funnel strategy for using solar energy to produce high-value mono-functional products from biomass.
研究领域:
化学
·
可再生能源
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
Materials Today Sustainability
·
2023
·
IF 7.8
G. Yang,H. Sun,R. Liu,J. Shi,X. Tong
Heterogeneous catalytic and selective C–C bond cleavage is considered as the important way for the production of high valuable compounds from large-molecule-weight feedstock . In this article, a sustainable and efficient aerobic oxidative C–C bond cleavage of lignin models is developed with the bismuth-based solid catalyst. Therein, the flower-like Bi 2 O 2 CO 3 exhibits a high photocatalytic efficiency in the reaction medium combined of n-butanol and tetramethylammonium bromide. For example, the selective oxidative C–C bond cleavage of 1-phenyl-ethane-1, 2-diol has been successfully carried out, where the substrate conversion and the selectivity of benzaldehyde was 95% and 99%, respectively. The study exhibited that the amount of oxygen vacancies plays a significant role on the photocatalytic selective aerobic oxidative cleavage processes. Moreover, the selective aerobic oxidative C–C bond cleavage of different lignin models was investigated, and all the yields of corresponding products are more than 90% with this photocatalytic system. Furthermore, the used flower-like Bi 2 O 2 CO 3 can be recycled at least 5 times without the obvious decrease of catalytic activity .
研究领域:
催化化学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Small
·
2023
·Vol. 20
·期 3
·2304990
·
IF 13.3
Na Ye,Wenchao Sheng,Riguang Zhang,Binhang Yan,Zhao Jiang,Tao Fang
The splitting of the C–C bonds of ethanol remains a key issue to be addressed, despite tremendous efforts made over the past several decades. This study highlights the enhancement mechanism of inexpensive NbN-modified Pd 1 Sn 3 -NbN/C towards the C–C bonds cleavage for alkaline ethanol oxidation reaction (EOR). The optimal Pd 1 Sn 3 -NbN/C delivers a catalytic activity up to 43.5 times higher than that of commercial Pd/C and high carbonate selectivity (20.5%) toward alkaline EOR. Most impressively, the Pd 1 Sn 3 -NbN/C presents good durability even after 25 200 s of chronoamperometric testing. The enhanced catalytic performance is mainly due to the interfacial interaction between PdSn and NbN, demonstrated by multiple structural characterization results. In addition, in situ ATR-SEIRAS (Attenuated total reflection-surface enhanced infrared absorption spectroscopy) results suggest that NbN facilitates the C–C bonds cleavage towards the alkaline EOR, followed by the enhanced OH adsorption to promote the subsequent oxidation of C1 intermediates after doping Sn. DFT (density functional theory) calculations indicate that the activation barriers of the C–H bond cleavage in CH 3 CH 2 OH, CH 3 CHOH, CH 3 CHO, CH 3 CO, CH 2 CO, and the C–C bond cleavage in CH 3 CO, CH 2 CO, CHCO are evidently reduced and the removal of adsorbed CH 3 CO and CO becomes easier on the PdSn-NbN/C catalyst surface.
研究领域:
材料科学
·
电化学
·
表面科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
STAR Protocols
·
2022
·
IF 0
Fukai Xie,Hongliang Liang,Wen Dai
Summary The cleavage and functionalization of carbon-carbon (C–C) bonds has emerged as a powerful tool for preparing value-added chemicals. In this protocol, we describe the preparation of amorphous manganese oxide and its application as a heterogeneous catalyst in the direct synthesis of amides via successive cleavage and amidation of C–C bonds in alcohols. Furthermore, we describe how a slight modification of reaction conditions allows for the cleavage and cyanation of alcohols to access sterically hindered nitriles. For complete details on the use and execution of this protocol, please refer to He et al. (2022) .
研究领域:
化学
·
催化科学
✓ 已验证
DOI
PubMed
危险品化学品经营许可证（带存储）