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
Catalysis Science & Technology
·
2024
·
IF 4.4
Chengyang Sun,Yong Guo,Xiaohui Liu,Yanqin Wang
Plastics with inter-monomer C–C bond linkages comprise more than 70% of all plastics production, but their chemical recycling and upcycling usually require harsh conditions due to the inertness of C–C bonds, hindering their utilization efficiency. Here, we develop an oxidative upcycling strategy to convert polystyrene (PS) waste into benzoic acid over a NiO/TiO2 catalyst. This system is carried out in an environmentally friendly manner in an aqueous phase by using air as the oxidant, and up to 51.1% carbon yield of benzoic acid is obtained at 200 °C, 1 MPa air and 18 h. The conversion of real-life PS plastics is also successfully demonstrated. The reaction mechanism is further investigated by capturing radicals and intermediates during the oxidative reaction, confirming ·O2− radicals as the reactive oxygen species. A possible oxidative mechanism was proposed: the ·O2− radicals first activated the C–H bonds in the aliphatic portion of PS to generate carbonyl groups or CC bonds; then, through attack of the weak CC bonds, the polymer was constantly depolymerized to smaller oxygenated oligomers, dimers and finally the target product, benzoic acid. This work has provided a promising and green polystyrene upcycling strategy.
研究领域:
化学工程
·
环境科学
·
材料科学
✓ 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
Catalysts
·
2022
·Vol. 12
·期 5
·460
·
IF 4.501
Yifan Zheng,Lijun Lu,Wei Chen,Anmin Zheng,Aiwen Lei,Abhishek Dutta Chowdhury
Global warming and rising waste content collectively accelerate the development of renewable-derived ‘low-carbon’ chemical technologies. Among all abundant renewables, marine-/food-waste-derived chitin, the only nitrogen-containing sustainable biomass, contains the uniqueN-acetylglucosamine units, which could be synthetically manipulated to a plethora of organonitrogen chemicals. Herein, we report the efficient one-step catalytic valorization of chitin toN-acylethanolamine over cost-effective Ni/CeO2-based materials, which interestingly demonstrate shape-based reactivity based on CeO2supports. In general, all three catalysts (Ni on cubic-, rod-, and polyhedral-shaped CeO2supports) were active for this reaction, but they differed in their catalytic efficiency and time-monitored reaction profiles. Herein, Ni on cubic-shaped CeO2delivered relatively better and stable catalytic performance, along with its rod-shaped counterpart, while the polyhedral CeO2-based material also delivered decent performance. Such interesting catalytic behavior has been corroborated by their physicochemical properties, as revealed by their characterization studies. Herein, to establish an appropriate structure-property-reactivity relationship, multimodal characterization techniques and control mechanistic experiments have been performed. This work demonstrates a concept to reduce the consumption of primary carbon resources and increase the utilization of secondary waste materials to facilitate a smooth transition from a linear economy (cf. cradle-to-grave model) to a circular economy (cf. cradle-to-cradle model).Keywords:chitin;waste valorization;heterogeneous catalysis;ceria;functionalization of C–C bonds
研究领域:
生物化学
·
环境科学
·
催化化学
✓ 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
ACS Catalysis
·
2017
·
IF 10.614
Tingting Hou,Nengchao Luo,Hongji Li,Marc Heggen,Jianmin Lu,Yehong Wang,Feng Wang
Selective cleavage of C–C bonds is pursued as a useful chemical transformation method in biomass utilization. Herein, we report a hybrid CuOx/ceria/anatase nanotube catalyst in the selective oxidation of C–C bonds under visible light irradiation. Using the lignin β-1 model as a substrate offers 96% yields of benzaldehydes. Characterization results by high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and energy-dispersive X-ray spectroscopy element (EDX) mapping reveal that CuOx clusters are highly dispersed on the exposed anatase surface as well as on the nanosized ceria domains. In-depth investigations by Raman and ultraviolet visible diffuse reflectance spectra (UV−vis DRS), together with density functional theory (DFT) calculations, further verify that the CuOx clusters present on the ceria domains increase the concentration of surface defects (Ce3+ ions and oxygen vacancies) and accordingly improve the photocatalytic activity (Yang character); the CuOx clusters decorating on anatase suppress the side reaction (oxy-dehydrogenation without C–C bond cleavage) because of an upward shift in the valence band (VB) edge of anatase (Yin character). Mechanism investigation indicates hydrogen abstraction from β-carbon by photogenerated holes is a vital step in the conversion.
研究领域:
化学
·
材料科学
·
催化反应
✓ 已验证
DOI
高影响因子
BIOMACROMOLECULES
·
2020
·
IF 6.092
Caicai Jiao,Lilong Gao,Hui Zhang,Bing Yu,Hailin Cong,Youqing Shen
Hydrogels have a wide range of applications in the fields of biomedicine, flexible electronics, and bionics. In this study, injectable and self-healable hydrogels were first prepared based on a dynamic covalent C═C bond formed via the Knoevenagel condensation reaction between poly(ethylene glycol) dicyanoacetate and water-soluble poly(vanillin acrylate). Three kinds of catalysts (phosphate buffer, zeolitic imidazolate framework-8, and tertiary amine) were used in Knoevenagel condensation for preparing hydrogels. All hydrogels in this study could be formed in situ, and their gelation time ranged from seconds to minutes. The properties and application of hydrogels could be customized according to the type of catalyst employed. 3-[4,5-Dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT) results indicated that all the components and hydrogels exhibited low toxicity, and the hydrogels could be used as 3D cell culture scaffolds. Because of the dynamic covalent C═C bond formed by Knoevenagel condensation, the resultant hydrogels were found to be dynamic and showed good self-healing properties. This work presents a new dynamic covalent chemistry for the preparation of self-healable materials.
研究领域:
生物医学工程
·
材料科学
·
组织工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Green Energy & Environment
·
2022
·
IF 12.781
Bolin Wang,Chunxiao Jin,Shujuan Shao,Yuxue Yue,Yuteng Zhang,Saisai Wang,Renqin Chang,Haifeng Zhang,Jia Zhao,Xiaonian Li
Rational design of catalytic sites to activate the C C bond is of paramount importance to advance acetylene hydrochlorination. Herein, Cu sites with electron-rich and electron-deficient states were constructed by controlling the impregnation solutions. The π electrons flowing from acetylene to Cu site are facilitated over the electron-deficient Cu sites, achieving high activation of C C bond. The contradiction between the increased activation of acetylene required for enhanced catalytic activity and the resistance of Cu site to reduction by acetylene required for maintaining catalytic stability can be balanced by establishing strong interactions of Cu site with pyrrolic-N species. The catalytic activity displays a volcano shape scaling relationship as a function of Cu particle size. Tribasic copper chloride is concomitantly generated with the construction of electron-deficient Cu sites. The H–Cl bond of HCl can be activated over the tribasic copper chloride, accelerating the surface reaction of vinyl chloride production. This strategy of inducing electron deficiency provides new insight into the rational design of catalysts for the synthesis of vinyl chloride with a high catalytic performance.
研究领域:
化学催化
·
材料科学
·
工业化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Meifang Cao,Yuqiao Ma,Tao Ruan,Lifeng Li,Bo Chen,Xueqing Qiu,Di Fan,Xinping Ouyang
The cleavage of C-O bonds in lignin depolymerization was made great progress, but the cleavage of C-C bonds still face challenges. An atomically dispersed Pt loading of 3.30 wt% catalyst, Pt/Nb 2 WO 8 , was prepared by the pyrolysis of ammonium niobate oxalate and sodium tungstate dihydrate with ammonium carbonate as the template. It is found that the decomposition of ammonium carbonate and the doping of W species promoted the orderly growth of niobium tungsten oxide crystals with oxygen vacancy and the formation of a regular porous structure, which was conducive to the dispersion of Pt particles. Pt/Nb 2 WO 8 efficiently cleaved β-O-4, β-1, α-1 and 5–5 bonds. The yield of aromatic monomers for lignin depolymerization reached as high as 49.08% over Pt/Nb 2 WO 8 . Experiments combined with density functional theory calculations revealed that the excellent activity of the Pt/Nb 2 WO 8 catalyst was attributed to the cooperation of atomically dispersed Pt sites and support near the interface. The atomically dispersed Pt species enhanced the dissociation of H 2 , and the Nb 2 WO 8 support with abundant B acid sites provided by W doping and oxygen vacancies activated C-O and C-C bonds of lignin in the reaction. The homogeneous cleavage of C-C bonds dominated the deconstruction of β-1, α-1 and 5–5 bonds. This methodology opens up a facile strategy for the design of atomically dispersed Pt/Nb 2 WO 8 catalyst with higher Pt loading and excellent catalytic activity to the cleavage of both C-O and C-C bonds in lignin.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
ChemistrySelect
·
2024
·Vol. 9
·期 28
·e202402061
·
IF 1.9
Jiankang Ou,Haoyu Liu,Zeguo Fang,Qian Zhang,Dong Li
Graphical Construction of C−C bonds of alkyl-substituted naphthoquinones through C−H/C−H cross dehydrogenation coupling of naphthoquinones with acetone and 1,3-dicarbonyl compounds was developed. A direct C−H alkylation of naphthoquinones with acetone and 1,3-dicarbonyl compounds was developed to construct C−C bonds of alkyl-substituted naphthoquinone derivatives. It proceeded through an oxidative radical cross dehydrogenation coupling process under simple and mild conditions. This method provides a facile and efficient route for synthesis of functionalized naphthoquinones from readily available feedstocks.
研究领域:
有机化学
·
合成化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）