ACS Catalysis
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2024
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IF 11.3
Zongyi Huang,Pengfei Sun,Huizhen Zhang,Haikun Zhang,Shuhong Zhang,Zhou Chen,Xiaodong Yi,Shunji Xie
The integration of solar-driven H2 evolution with the selective conversion of biomass-derived alcohols into value-added chemicals has gained significant attention for full use of electrons and holes. We develop a dual-functional photocatalyst for highly selective oxidation of the Cα–H bond of benzyl alcohol to C–C coupled products (hydrobenzoin and deoxybenzoin), in cooperation with H2 evolution, using point-to-face interface engineering by decorating CdS quantum dots on Zn2In2S5 nanosheets (CdS QDs/Zn2In2S5 NS). The CdS QDs/Zn2In2S5 NS exhibit a high H2 evolution rate of 13 mmol g–1 h–1 and C–C coupled products formation rate of 10.8 mmol g–1 h–1 with 96.3% selectivity. Benzyl alcohol conversion achieves 91% with an 89% yield of C–C coupled products in gram-scale. The introduction of CdS enhances the interfacial contact, facilitating the efficient spatial separation of photogenerated electron–hole pairs and providing active sites for H2 evolution. In situ characterization and DFT calculation reveal that the carbon-centered radical •CH(OH)C6H5, generated by abstracting the Cα–H bond of benzyl alcohol, is the reactive intermediate in the photocatalytic C–C coupled process.
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Advanced Powder Materials
·
2025
·
IF 24.9
Yang Li,Bin Sun,Ying Li,Chong Zhang,Pu-Jun Jin,Xin Wang,Bao Yu Xia,Yu Chen,Xuan Ai
The large-scale implementation of direct ethylene glycol fuel cells (DEGFCs) relies on the design of catalysts that possess exceptional activity, durability, and efficient C–C bond breaking ability. However, Pt and Pd-based nanomaterials continue to face challenges of low selectivity and slow reaction kinetics in driving the complete oxidation of ethylene glycol to CO 2 . In this work, a facile one-pot reduction method is reported for controllable synthesis of PtBi nanodendrites (PtBi-NDs) composed of ultrathin bimetallene subunits. In alkaline media, the composition optimized PtBi-NDs demonstrate outstanding activity and strong resistance to CO poisoning during the ethylene glycol oxidation reaction (EGOR). The PtBi-NDs show 5.8-fold higher mass activity, enhanced stability, and superior C1 selectivity relative to commercial Pt nanoparticles (Pt c-NCs). Most strikingly, PtBi-NDs deliver a higher power density (8.3 mW cm –2 ) than Pt c-NCs in DEGFCs. The theoretical analysis and experimental measurements explain that the introduction of Bi element into Pt induces d–p orbital hybridization and promotes electron transfer from Bi to Pt, thereby facilitating C–C bond cleavage and boosting EGOR kinetics. This work establishes an effective strategy for constructing Pt-based ultrathin bimetallenes and offers fundamental insights into boosting EGOR performance via d-p orbital hybridization.
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Nature Communications
·
2025
·Vol. 16
·期 1
·1-9
·
IF 15.7
Lu Zong-Bin,Peng Shun-Ran,Wang Zhe,Xiong Yu,Xia Lei,Chen Guang,Nie Xuan,Hong Chun-Yan,Zhang Ze,You Ye-Zi
Developing high-performance CO 2 -based polymers is promising to address the challenges of CO 2 sequestration and the environmental impact of petroleum-based plastics. The δ-lactone 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one and its derivatives, synthesized from CO 2 with 1,3-butadiene, have emerged as very promising CO 2 -derived monomers. However, their general ring-opening polymerizations face challenges with thermodynamics and kinetics, generally resulting in long reaction times, low conversions, and low-molecular-weight polyesters with poor mechanical properties. Herein, we report a dual isomerization-driven cationic ring-opening polymerization (DI-CROP) of a CO 2 -derived thionolactone, 3-ethyl-6-vinyltetrahydro-2H-pyran-2-thione, in which the relayed S/O and vinyl isomerizations significantly enhance polymerization activity, enabling the rapid synthesis of high-molecular-weight CO 2 -based polythioesters, achieving near-quantitative conversion within just a few minutes. Also, the relayed S/O and vinyl isomerizations in DI-CROP can easily migrate C=C substituents on the ring of thionolactone into its backbone. These features further enable the production of sustainable CO 2 -based materials through efficient copolymerization and post-polymerization functionalization. This study enriches the realm of isomerization-driven polymerizations, and provides a new synthetic approach to CO 2 -derived polymeric materials.
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BIOMASS & BIOENERGY
·
2026
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IF 7
Weijie Shen,Li Dong,Shuoqi Pei,Guoqiang Ding,Shanhui Zhu,Yueqing Wang,Guangping Lei,Yulei Zhu
Tandem isomerization and decarbonylation increased furfural yield from 34.4% to 67.9%. • Framework Sn location was governed by T-vacancy distribution in dealuminated H-beta. • Open Sn sites at pore mouths improved furfural selectivity. The asymmetric C-C bond scission of C6 glucose to C5 furfural via a “C5 + C1” retro-aldol pathway represents a promising and important route for the valorization of bio-based sugar resources. However, this transformation still faces major challenges in achieving high selectivity and efficiency, as stable glucopyranose tends to undergo side reactions leading to oligomeric humins. In this work, to enhance furfural yield, Sn atoms were incorporated into the framework of dealuminated H-beta zeolite to construct synergistic active sites for coupling isomerization and decarbonization reactions. The catalytic performance was found to be highly sensitive to the type, spatial location, and coordination environment of framework Sn species. Based on Low-Energy Ion Scattering (LEIS) and X-ray absorption fine structure (XAFS) results, it is demonstrated that open Sn sites located at the pore mouths of H-beta zeolite are conducive to the conversion of glucose into furfural via coupled isomerization-decarbonization pathways. Accordingly, Sn-Al-beta-C, which possesses the highest proportion of open Sn sites, achieves the highest furfural yield of 67.9% at nearly complete glucose conversion, markedly outperforming H-beta (34.4%) and the corresponding physical mixtures. The ratio of open to closed Sn sites can be regulated by controlling the deposition of Sn (IV) species at the pore mouths of H-beta zeolite. The results of this work demonstrate the feasibility of constructing metal–acid bifunctional sites for the direct conversion of glucose to furfural and provide valuable insights for the rational design of efficient metal-modified zeolite catalysts.
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ACS Applied Materials & Interfaces
·
2025
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IF 8.2
Shuang Wei,Sheng Zhong,Chao Bao,Linbo Huang,Kexin Li,Ruirui Wang,Bin He,Ruirui Zhang,Ruixia Liu
The selective electrocatalytic oxidation of glycerol to high-value C2–C3 chemicals offers a promising approach to glycerol overproduction, while it struggles with precise C–C cleavage and limited selectivity from multiple pathways. Regulating the adsorption capacity of glycerol oxidation intermediates and the degree of C–C bond cleavage through the interfacial electronic structure of electrocatalysts is crucial for controlling C2–C3 selectivity. Herein, a self-supported p-n heterojunction catalyst (Co3O4/CeO2) is developed for the efficient electrocatalytic oxidation of glycerol to C2 chemicals, achieving a glycolic acid selectivity of 42%, with a yield of 19.6 μmol cm–2 h–1. The built-in electric field enables rapid interfacial charge transfer from CeO2 to Co3O4, which leads to the upshifted d-band center of active Co3O4. Electrochemical characterization and theoretical calculations demonstrate that the heterojunction promotes the adsorption of hydroxyl species and glycerol, thereby enhancing the activity of the glycerol oxidation reaction (GOR). Concurrently, the optimized electron cloud distribution of Co3O4 active sites strengthens the adsorption of oxygen-containing intermediates while weakening the adsorption of glycolic acid and suppresses the further cleavage of C–C bonds, thus increasing glycolic acid selectivity. This study clarifies the redox kinetic adsorption regulation mechanism of the Co3O4/CeO2 heterojunction catalyst and provides a highly promising electrocatalyst design strategy for the production of high-value-added C2 products via glycerol oxidation.
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Catalysis Science & Technology
·
2023
·Vol. 13
·期 6
·1748-1754
·
IF 5
Shaoyuan Guo,Xinli Tong,Lingwu Meng,Guobao Yang
Selective oxidative C–C and C–O bond cleavage is of significance to the efficient utilization of biomass and biomass-derived platform compounds. In this work, the selective oxidative cleavage of C–C and C–O bonds has been developed with an iron-based catalyst (Fe–N–C) in the presence of molecular oxygen. Specifically, the β-O-4 lignin model compound was successfully converted to phenol and methyl benzoate in a methanol solvent, where the substrate conversion was 95.0% and the yields of phenol and methyl benzoate were 94.9% and 63.7%, respectively, when the reaction was performed with the Fe–N–C-850 catalyst at 120 °C for 4 h. Also, the oxidative transformations of other lignin models to phenols and methyl benzoates were achieved. Further investigations showed that the existence of the Fe3C phase in the catalyst plays an important role in the aerobic oxidative cleavage of C–C and C–O bonds in the β-O-4 lignin model.
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CERAMICS INTERNATIONAL
·
2022
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IF 5.532
Ze Zhang,Cunqian Fang,Yuanqi Weng,Xiao Luo,Qizhong Huang,Huiping Hu
Graphene was introduced into C/C–SiC composites via pressureless impregnation to enhance the mechanical and thermal properties of the composites. The effects of various graphene contents on the mechanical and ablative performances of C/C–SiC composites were investigated. The results showed that the ultimate bending stress and compressive stress of the C/C–SiC composites increased by 28.98% and 23.64%, respectively, after adding 7.25% graphene. Moreover, the ablation rates of the composites were vastly decreased after adding a slight graphene content (2.13%). However, the ablation rates increased with increasing of graphene content, indicating that the benefit of introducing graphene on the ablation property decreased, which was mainly ascribed to the relative reduction in the SiC content. As a result, introducing slight graphene into C/C–SiC composites had the greatest benefit on the anti-ablation performance.
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ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Qifeng Chen,Guoming Gao,Huailin Fan,Jie Zheng,Lulu Ma,Yanyu Ding,Yanfen Fang,Ran Duan,Xiaofeng Cao,Yanchuan Guo,Dongge Ma,Xun Hu
The surface property of a photocatalyst, including surface acid sites and oxygen vacancies, plays a pivotal role in photocatalytic organic synthesis reactions. Benzoin isopropyl ether (BIE) is usually produced via polycondensation of benzaldehyde and catalyzed with highly toxic cyanide. Here, we report a green photocatalytic approach for the selective synthesis of BIE over WO3 driven by a green-light-emitting diode. The improved photocatalytic activity can be attributed to the synergy of oxygen vacancies (VOs) and acid sites over N-doped WO3 nanobelts. The results revealed that reactant molecules were predominantly adsorbed and activated on surface oxygen vacancies (VOSs) and the Brønsted acid promoted the etherification reaction; the introduction of VOs and nitrogen altered the band structure and electronic properties, resulting in improved photocatalytic activity. Our work provides an efficient approach to the selective photocatalytic synthesis of organics over photocatalysts with finely tuned surface properties and band structures via defect and doping engineering.
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ACS Applied Materials & Interfaces
·
2020
·
IF 8.758
Xin-bo Xiong,Chun Liu,Xin-Ye Ni,Cai-qing Liang,Xie-rong Zeng
Hydroxyapatite (HA) coatings directly deposited by hydrothermal electrochemical technology (HET) onto carbon/carbon (C/C) composites exhibited a catastrophic failure occurring at the interface of the HA and C/C. To overcome this problem, a polyvinyl alcohol (PVA)/graphene oxide (GO) interlayer (P/G interlayer) was applied on the (NH4)2S2O8-pretreated C/C substrate (named P/G-C/C) by using a dipping method. Subsequently, a calcium phosphate coating was deposited on P/G-C/C, shortened as M-P/G-C/C, by HET, and then converted into HA coating (abbreviated as HA-P/G-C/C) through posthydrothermal treatment. For comparison, HA coating was prepared onto C/C without a P/G interlayer through the same process, which was denoted as HA-C/C. The composition, microstructure, and morphology of the samples were characterized by X-ray diffractometry (XRD), energy-dispersive spectroscopy (EDS), scanning electron microscopy (SEM), Raman spectra, Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS). The adhesive performance of the coatings on C/C was measured by a scratch test. Finally, an in vitro bioactivity of the coatings was evaluated in a simulated body fluid solution at 37 °C. Results showed no apparent differences in the morphology and phase of the posttreated coatings, both of which are composed of a dense structure containing needle-like HA crystals. However, the HA-P/G-C/C sample possessed a higher Ca/P ratio and denser interface, thereby exhibiting higher adhesive performance and better bioactivity. The adhesive strength of the HA-P/G coating was observed at a critical load of 41.04 N, which increased by 29.3% relative to the HA coating. Moreover, the failure site was on the HA-P/G coating rather than at the interface. The enhanced adhesive performance was ascribed to the PVA/GO-repairing pits on C/C and PVA and GO toughening effects on the HA coating. In vitro and in vivo tests revealed no statistical significance for the two HA-coated C/C samples, although the HA-P/G coating exhibited better bioactivity, inducing the growth of bonelike apatite than the HA coating.
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Molecular Catalysis
·
2020
·
IF 3.687
Yang Zhong,Bo Zhou,Lijun Wang
Fe/FeO x embedded in LDH was prepared by reducing the pre-synthesized [Fe(C 2 O 4 ) 3 ] 3− anions intercalated LDH and used as a multi-functional catalyst for synthesis of C7-C9 compound via transfer hydrogenation between furfural (C5) and short-chain alcohols (C2-C4) and a subsequent aldol reaction of furfural with intermediate short-chain aldehydes in the absence of a homogeneous base with furfuryl alcohol as a byproduct. Screening reaction conditions, evaluation and improvement of the cyclic catalytic performance, and determination of catalytically active components were performed, and the results demonstrated that both high conversion and high selectivity to the C C bond forming product can be obtained under a non-oxidizing atmosphere of Ar or H 2 /Ar mixed gas, a reaction temperature of 140 °C and a reaction time of 4 h; the catalyst was easily deactivated during the cycle experiments, however, its catalytic stability can be effectively improved by depositing Ni with weak reducibility on the surface of Fe nanoparticles at the cost of reducing partial catalytic activity. Fe/FeO x together with LDH as a whole proved to be effective in catalyzing the transfer hydrogenation reaction and the support LDH imparted basic catalytic function to the composite realizing the aldol reaction in the absence of a homogeneous base.
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ACS Omega
·
2019
·
IF 2.584
Jing Wang,Aisen Li,Shuping Xu,Chongping Song,Yijia Geng,Ling Ye,Houyu Zhang,Weiqing Xu
The mixed π–π packing of the donor (D) and acceptor (A) molecules is the highlighting feature of the intermolecular interactions following charge transfer (CT) issues in organic cocrystal systems. There is an inverse relationship between the D–A interplanar distance and the intermolecular CT interaction. However, the D–A C–C surface close contact (relative areas) on the intermolecular CT interactions in organic cocrystal systems is rarely investigated. Herein, we designed and constructed a novel cocrystal and its solvate cocrystal. The structural and electrostatic potential analyses suggest that the solvation destroys the N–H···N hydrogen bond interaction between phenothiazine (PTZ) and 1,2,4,5-tetracyanobenzene (TCNB), which causes the TCNB molecules to have a 90° rotation along the normal axis of the PTZ plane. Thus, the D–A C–C surface close contact is enlarged, strengthening the intermolecular π–π stacking interactions and intermolecular CT interaction between PTZ and TCNB, which are further evidenced by the absorption and Raman spectroscopic analyses. This study provides rare evidence of the enlarged C–C surface close contact in the mixed packing between D and A that greatly contributes to the intermolecular CT interaction in a D–A cocrystal system. It also provides a deeper understanding of the role of solvation in the structure–property relationship of organic cocrystal materials.
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ACS Catalysis
·
2018
·
IF 11.384
Huifang Liu,Hongji Li,Jianmin Lu,Shu Zeng,Min Wang,Nengchao Luo,Shutao Xu,Feng Wang
Photocatalysis is a potentially promising approach to harvest aromatic compounds from lignin. However, the development of an active and selective solid photocatalyst is still challenging for lignin transformation under ambient conditions. We herein report a mild photocatalytic oxidative strategy for C–C bond cleavage of lignin β-O-4 and β-1 linkages using a mesoporous graphitic carbon nitride catalyst. Identifications by solid-state NMR techniques and density functional theory (DFT) calculations indicate that π–π stacking interactions are most likely present between the flexible carbon nitride surface and lignin model molecule. Besides, low charge recombination efficiency and high specific surface area (206.5 m2 g–1) of the catalyst also contribute to its high catalytic activity. Mechanistic investigations reveal that photogenerated holes, as the main active species, trigger the oxidation and C–C bond cleavage of lignin models. This study sheds light on the interaction between complex lignin structures and the catalyst surface and provides a new strategy of photocatalytic cleavage of lignin models with heterogeneous photocatalysts.
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