RARE METALS
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2025
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IF 11
Chen Taoran,Qin Tian,Sun Hongli,Su Chenliang
Photocatalytic oxidation of toluene to valuable benzaldehyde offers a promising pathway for sustainable production of fine chemicals and pharmaceuticals. In this process, photogenerated holes play a crucial role in C(sp 3 )-H bond dissociation. However, the photocatalytic performance of current photocatalysts is often hindered by the low separation and transfer efficiency of photogenerated charges. In this work, we presented a perovskite-based heterostructure via in situ growth of defective WO 3- x nanosheets on Cs 2 AgBiBr 6 nanoparticles for photocatalytic toluene transformation. In situ Fourier transform infrared spectroscopy tests proved the introduction of oxygen-deficient WO 3- x component enhanced the chemisorption of molecular oxygen. The in situ electron paramagnetic resonance and 4-chloro-7-nitro-1,2,3-benzoxadiazole fluorescence measurements further confirmed the presence of oxygen vacancies, and the formation of heterostructure synergistically accelerated the formation of the superoxide radicals and the transfer of photogenerated charge carriers. Under visible light irradiation, Cs 2 AgBiBr 6 /WO 3- x photocatalyst could effectively oxidize toluene toward benzaldehyde with a conversion rate of 9020 μmol g −1 h −1 , which was a 3.5-fold increase over that of the unmodified Cs 2 AgBiBr 6 . Graphical abstract
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Nature Communications
·
2026
·
IF 18.1
Bing-Liang Leng,Xiu Lin,Hou-Yan Dong,Qi-Yuan Li,Shi-Nan Zhang,Jie-Sheng Chen,Xin-Hao Li
Recent studies on the electrocatalytic oxygen transfer from water to organic compounds have gained significant attention due to their sustainability and selectivity. However, the direct coactivation of inert hydrocarbons and water typically requires high oxidation potentials, leading to oxygen evolution reactions and low Faradaic efficiencies. Herein, a Ni-activated tungsten-oxygen covalency anode is designed for the efficient oxygen transfer from water to benzylic C(sp 3 )–H bonds via a Ni-regulated interfacial water structure between the anode and electrolyte. Both experimental and theoretical results reveal the critical role of W–O covalency sites with Ni-heteroatoms for boosting efficient oxygen transfer via breaking the dense interfacial hydrogen bond network and inhibiting the undesired oxygen evolution reactions, facilitating the coactivation of oxygen species and C(sp 3 )–H bonds. Thus, a Faradaic efficiency of > 56% in a water-involved system has been achieved. This work provides important insight into designing electrocatalytic systems for inert C–H oxidation. The direct coactivation of inert hydrocarbons and water typically requires high oxidation potentials. Here, the authors report that a Ni-activated tungsten-oxygen covalency anode is designed to steer the oxygen transfer from water to benzylic C(sp 3 )–H bonds via Ni-regulated interfacial water structure.
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高影响因子
TETRAHEDRON
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2021
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IF 2.457
Xiao-Long Su,Sheng-Peng Jiang,Liu Ye,Guo-Xing Xu,Ji-Jun Chen,Qiang-Shuai Gu,Zhong-Liang Li,Xin-Yuan Liu
A general copper-catalyzed C( sp 3 )−C( sp 2 ) cross-coupling of (hetero)benzyl bromides with the air- and moisture-stable aryl nucleophiles has been developed, providing a facile access to pharmaceutically useful 1,1-di(hetero)arylalkane and 1-aryl-1-heteroarylalkane scaffolds. Critical to the success is the utilization of a proline-based N,N,P-ligand to enhance the reducing capability of copper, thus easily converting benzyl bromides to the corresponding radical species via a single-electron transfer process under ambient conditions. The reaction features a broad substrate scope, covering (hetero)arylboronate esters, oxadiazoles , and benzo[ d ]oxazoles, as well as primary and secondary (hetero)benzyl bromides with excellent functional group tolerance.
研究领域:
有机化学
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药物化学
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Catalysts
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2023
·Vol. 13
·期 4
·726
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IF 3.9
Jun Qiao,Kai Zheng,Zhiwei Lin,Huiye Jin,Wenbo Yu,Chao Shen,Aiquan Jia,Qianfeng Zhang
The exploration of inexpensive and stable heterogeneous catalysts for C–S coupling reactions remains a challenging issue. Herein, we successfully prepared a new biomass-derived copper catalyst and applied it to the selective C(sp3)–H-directed sulfonylation of ketone hydrazones with commercial sodium sulfinates. The catalyst was characterized using different spectroscopic and microscopic techniques. Importantly, the prepared biomass-supported Cu catalyst catalyzed the C–S coupling reaction with considerably high activity. A variety of aryl and alkyl sulfinates were converted to the corresponding sulfones with good yields. In particular, the heterogeneous catalyst could be recovered easily after the synthesis and consecutively used at least five times with no appreciable decrease in the catalytic activity. Lastly, the copper catalyst is expected to have further applications in organic reactions catalyzed by Cu/CuO2.Keywords:biomass-derived;copper catalysts;heterogeneous;C–S coupling
研究领域:
有机化学
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催化化学
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ORGANIC & BIOMOLECULAR CHEMISTRY
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2026
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IF 2.8
Lin Chen,Shuang Xu,Zhiming Chen
Direct α-C(sp3)−H arylation of 4-aminopyrazolones involving arynes, enabled by dual phase-transfer catalysis and ultraviolet irradiation, has been developed. The dual phase-transfer catalytic pathway powered by triaminocyclopropenium salts gave rise to the generation of structurally diverse 4-amino-4-arylpyrazolones in moderate to excellent yields, while the photochemical protocol furnished the products with moderate yields. Notably, these products are tentatively proposed as candidates for carbamate pesticides based on the preliminary structural analysis. The synthetic potentials of the methods were shown by gram-scale reactions, and the possibilities for greater structural diversity of the product were highlighted by derivatizations. The results of control experiments indicated that the timely capture of the transient arynes by the activated 4-aminopyrazolone nucleophiles is the key to the success of the reactions.
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CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Xuefeng Zhou,Xiaohai Zheng,Jinyu Li,Lijuan Shen,Xiaoyang Pan,Xuhui Yang,Min-Quan Yang
Photocatalytic selective oxidation of benzylic C( sp 3 )-H bonds to high-value oxygenates holds great potential for sustainable organic synthesis, yet remains challenging due to inefficient charge separation and limited substrate activation over conventional photocatalysts. Herein, a C 3 N 4 /PMA 2 PbBr 4 heterojunction is rationally designed via an anti-solvent strategy, integrating 2D PMA 2 PbBr 4 with π-conjugated C 3 N 4 . Experimental and theoretical analyses reveal that the internal electric field induced by band alignment drives spatial charge separation, preserving the powerful holes in the valence band of PMA 2 PbBr 4 for direct C H bond activation and electrons in the conduction band of C 3 N 4 for efficient O 2 reduction. Notably, C 3 N 4 demonstrates enhanced toluene adsorption via π-π interactions, concentrating substrates at reactive interfaces. The synergistic interplay of optimized charge dynamics and molecules activation enhances hole-mediated C H cleavage and radical-driven further oxidation. Consequently, the optimized 5 % C 3 N 4 /PMA 2 PbBr 4 achieves a benzaldehyde production rate of 5783 μmol g −1 h −1 under visible light, outperforming pristine PMA 2 PbBr 4 by a factor of 1.7 and C 3 N 4 of 25.8.
研究领域:
光催化
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材料科学
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有机合成
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环境化学
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纳米技术
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Molecular Catalysis
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2024
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IF 3.9
Guili Luan,Guihua Yang,Hongyu Wang,Jiaxuan Li,Haojie Sun,Mengyao Sun,Changfei Shi,Shitao Yu,Ji-Jun Zou,Genkuo Nie
(Alkyl-)cyclohexane diols are of high value as industrial reagents and resources, but current producing methods are still unsustainable. Herein, a new method of producing (alkyl-)cyclohexane diols using lignin derived phenols with yield as high as 91.2 % by selective hydrogenolysis is firstly achieved over Nb 2 O 5 and Ni/MCM-41. The hydrogenolysis is completed by designing two-step reactions compositing of selective crack of C(sp 3 )-O bond and selective hydrogenation of benzene ring of lignin derived phenols to achieve a high selectivity. Nb 2 O 5 demonstrates superior activity and long-life time in C(sp 3 )-O bond cleavage compared to commercial solid acids. The robust catalytic performance was thoroughly analyzed through detailed characterization and attributed to the abundant oxygen vacancies produced, which lead more strong L acids and adsorb the methoxy group in lignin derived phenols and at the same time interact with the acid sites to facilitate the cleavage of the C(sp 3 )-O bond. The consequent selective hydrogenation of benzene ring is completed by Ni/MCM-41 easily. More lignin derived phenols are explored in this reaction with (alkyl-)cyclohexane diols universally synthesized. This work provides a new application of lignin derived phenols to synthesize value-added chemicals and makes contribution to sustainable development by biorefineries.
研究领域:
化学工程
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催化
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可持续化学
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生物化学
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ACS Applied Materials & Interfaces
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2021
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IF 9.229
Yefei Wang,Zhen Zhou,Liang Zhao,Cheng He,Wenlong Sun,Chunying Duan
The activation and transformation of inert alkyl C(sp3)−H bonds to obtain high-value fine chemicals by sustainable solar energy are of great significance. Herein, by incorporating IrIII–porphyrin into metal–organic frameworks (MOFs) to stabilize the highly active carbene, we reported a new approach to combining metallo- and photocatalysis to efficiently accelerate carbene migratory insertion and C–H bond activation via the radical coupling pathway for inert alkane functionalization. The in situ-formed carbene was restricted into the pores of MOFs to produce IrIII–carbene, allowing the first-time isolation and structural characterization of the IrIII–carbene intermediate which are not stabilized by a heteroatom. The product of the reaction, especially the cyclic ethers as substrates, suggested that the functionalization of the α position of the alkoxy group was favored. Additionally, the new approach could be extended to stabilize the metal carbene intermediates to realize C(sp3)−H bond alkylation and arylation.
研究领域:
化学
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材料科学
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催化反应
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高影响因子
Journal of Energy Chemistry
·
2025
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IF 14.9
Xiaoping Wang,Bowen Yang,Haoye Wang,Haixin Guo,Richard Lee Smith,Yaqiong Su,Xinhua Qi
Photocatalytic oxidative dehydrogenation of biomass feedstocks offers the possibility for synthesizing value-added chemicals, but the sluggish transport kinetics and rapid recombination of photogenerated charge carriers constrain photocatalysis efficiency. Spin-polarized photocatalysts, by accelerating the separation of photogenerated electrons and holes, offer a promising strategy for selective biomass valorization. Herein, polarization unit Mo was incorporated into ZnIn 2 S 4 (ZIS) with S-vacancy through Mo–S 4 coordination (Mo-Vs-ZIS) to enhance hole and proton-coupled electron transfer (PCET). Mo-Vs-ZIS spin polarized photocatalyst applied to 5-hydroxymethylfurfural (HMF) afforded a 2,5-diformylfuran (DFF) selectivity of 92.3% at a production rate of 1105.3 µmol g cat −1 h −1 , attributed to carrier transport and reaction processes. The Mo-Vs-ZIS photocatalyst efficiently (100 min) converted benzyl and furfuryl alcohols, aromatic alcohols bearing electron-rich substituents, and halogen-substituted aromatic alcohols into their corresponding aldehydes. Piezoelectric force microscopy (PFM) and Kelvin probe force microscopy analyses (KPFM) revealed that the full-space polarized electric field was formed to drive directional transfer of photogenerated carriers, facilitating bulk-to-surface charge separation. Moreover, Mo-Vs-ZIS showed high Bader charge transfer to O 2 , where Mo atomic sites functioned as an electron reservoir, driving the activation of O 2 to form •O 2 − , a kinetically favorable step for HMF oxidation and induced transfer of holes to activate C( sp 3 )–H bonds, which is a rate-determining step. Then, the critical step of PCET (•O 2 − +H + →•OOH) over Mo-Vs-ZIS gave •OOH for O–H activation to complete the reaction sequence. This spin-polarized modification strategy featuring atomic-level catalytic sites enables its application to other semiconductor photocatalysts for biomass conversion.
研究领域:
光催化
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材料科学
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化学工程
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生物质转化
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有机合成
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能源与环境科学
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半导体催化
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