JOURNAL OF ORGANIC CHEMISTRY
·
2021
·
IF 4.354
Yan-Ling Song,Bei Li,Zhen-Biao Xie,Dan Wang,Hong-Mei Sun
Iron-catalyzed oxidative amination of benzylic C(sp3)–H bonds with anilines bearing electron-withdrawing groups (EWGs) or electron-donating groups (EDGs) is realized based on simple variations of N-substituents on imidazolium cations in novel ionic Fe(III) complexes. The structural modification of the imidazolium cation resulted in regulation of the redox potential and the catalytic performance of the iron metal center. Using DTBP as oxidant, [HItBu][FeBr4] showed the highest catalytic activity for anilines bearing EWGs, while [HIPym][FeBr4] was more efficient for EDG-substituted anilines. This work provides alternative access to benzylamines with the advantages of both a wide substrate scope and iron catalysis.
研究领域:
有机化学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Molecular Catalysis
·
2024
·
IF 3.9
Guiyu Chen,Wei Liu,Shiqiang Wang,Yongxiang Miao,Zhibin Song
Quinazolinone-based boron difluoride (BF 2 ) complexes were developed for the synthesis of dihydroisoquinolones, 2-phenylisoindolinone, 1-isochromanone and diarylketone through α-C(sp 3 )-H photooxidation. Seven selected quinazolinone-based BF 2 complexes exhibited good activity for photooxidation reaction using air as oxidant. It is worth noting that quinazolinone-based BF 2 as photocatalysts do not require the introduction of halogen heavy atoms to improve catalytic activity. Mechanism exploration indicated these BF 2 catalysts may involve a single electron transfer (SET) mediated photoredox catalysis to achieve α-C(sp3)-H oxidation. These quinazolinone-based BF 2 catalysts with facile preparation and structural modifiability would be good choice for organic oxidative transformation in the future.
研究领域:
有机化学
·
光化学
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Yalin Yang,Zheyan Chen,Hanlin Huang,Yuxin Liu,Junhua Zou,Shuqi Shen,Jiawei Yan,Jinshui Zhang,Zanyong Zhuang,Zhongzhen Luo,Chengkai Yang,Yan Yu,Zhigang Zou
Halide perovskites and derivatives have been used as emerging photocatalysts due to their unique optoelectronic and structural diversity. However, compared with the well-explored photophysical processes for light-driven more energetic carriers to trigger redox reactions, catalytic effects on the surface of halide perovskite or their derivatives for chemical transformations between reactive species are seldom addressed, which is equally important for improving the efficiency for halide perovskite-based photocatalysts. Here, we demonstrate that Cs 3 Bi 2 Br 9 sites in the Cs 3 Bi 2 Br 9 /CdS heterojunction, not only participate in light-driven processes, but also play a vital role for the activation and conversion of key intermediates during C(sp 3 )-H bond transformation, via a more thermodynamically and kinetically favorable surface reaction pathway. Besides, various aromatic hydrocarbons can be effectively photocatalytic converted to corresponding aldehydes/ketones as major products. This work highlights the importance of surface catalysis mechanism in photocatalysis not only for halide perovskites but also for other semiconductors.
研究领域:
材料科学
·
化学工程
·
光化学
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Ganhua Qiu,Ting Wang,Xiaoli Li,Xueqin Tao,Benxia Li
A heterostructure photocatalyst consisting of BiOCl nanoplates and a bismuth-organic hybrid layer (alias BiCl3Br–CTA) was synthesized through a one-step solvothermal process. The BiOCl/BiCl3Br–CTA heterostructures exhibited broad light absorption and enhanced electron–hole separation efficiency. Moreover, the abundant oxygen vacancies (OVs) and superoleophilic surface endowed the photocatalyst with high abilities for adsorption and activation of O2 and toluene. Therefore, the BiOCl/BiCl3Br–CTA photocatalyst showed excellent activities for the C(sp3)–H bond oxidation of toluene under full-spectrum irradiation and visible light of simulated sunlight, which are 6.8-fold and 237.8-fold, respectively, than those of BiOCl nanoplates. The photocatalytic mechanism was revealed by a series of controlled experiments and in situ ESR detections. The selective oxidation of toluene was promoted by the synergy between the electrons in BiOCl for activating O2 and the holes in the BiCl3Br–CTA layer for activating the C(sp3)–H bonds. This research demonstrates an effective strategy to construct high-activity photocatalysts for challenging organic transformations.
研究领域:
材料科学
·
环境科学
·
催化化学
✓ 已验证
DOI
高影响因子
GREEN CHEMISTRY
·
2021
·Vol. 24
·期 1
·384-393
·
IF 10.182
Qi Zhang,Shouxin Liu,Xia Tian,Yidong Liu,Shiming Fan,Baibiao Huang,Andrew Whiting
A highly selective, green and sustainable chlorination of aliphatic C–H bonds is reported using MCln under the co-catalysis of visible light and nano-Cu@CuCl, which was synthesised via a one-step, hydrothermal strategy using copper(II) sulfate and D-glucose as the reducing agent in a KCl solution. A novel cascade method of producing Cl2 occurs in situ chlorinating C(sp3)–Hs, achieved through nano-Cu@CuCl catalysis using inorganic chloride MCln as a chlorine source under visible light and without the need for a strong oxidant. The reaction was applied to the chlorination of different alkylarene α-Hs and cyclic hydrocarbons C–HS and was developed for use in a photocatalytic serial reactor system which accomplished the chlorination of toluene α-Hs to give 92% conversion, 90% yield and 98% selectivity. Electron spin resonance (ESR) studies of DMPO-Cl. revealed that the reaction mechanism belonged to a free radical process.
研究领域:
有机化学
·
绿色化学
·
材料科学
✓ 已验证
DOI
高影响因子
Solar RRL
·
2021
·Vol. 5
·期 12
·2100559
·
IF 8.582
Hong-Hong Zhang,Zi-Chun Zhou,Yu-Jie Dong,Li Zhang,Hong-Yan Chen,Dai-Bin Kuang
Utilizing halide perovskites for photocatalytic aromatic C( sp 3 ) H bond activation remains a great challenge due to the serious recombination of photogenerated charge carriers and slow reaction dynamics of the materials themselves. Herein, a lead-free perovskite-based hybrid of Cs 3 Sb 2 Br 9 /g-C 3 N 4 nanosheet is constructed and applied for photocatalytic aromatic C( sp 3 ) H bond activation, which shows enhanced photocatalytic performance. By introducing ultrathin g-C 3 N 4 nanosheets as the heterogeneous nucleation sites, size-reduced and well-dispersed Cs 3 Sb 2 Br 9 nanocrystals can be obtained. The as-formed close contact and high-quality heterointerface between Cs 3 Sb 2 Br 9 and g-C 3 N 4 provides pathways for fast charge transfer which is beneficial to improve the separation efficiency of photogenerated electron−hole pairs. Under visible light irradiation, the Cs 3 Sb 2 Br 9 /g-C 3 N 4 hybrid photocatalyst can effectively oxidize toluene toward benzaldehyde and benzyl alcohol with a total conversion rate of 8346.8 μmol g −1 h −1 , which is 26.6- and 6.0-fold that of pure g-C 3 N 4 and Cs 3 Sb 2 Br 9 , respectively. This work demonstrates the potential of all-inorganic lead-free halide perovskite-based heterostructures for photocatalytic organic reactions.
研究领域:
材料科学
·
化学
·
光催化
·
纳米技术
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Tao Shan,Sunzai Ke,Xin Yang,Xuhui Yang,Bo Weng,Lijuan Shen,Min-Quan Yang
Photocatalytic selective oxidation of aromatic hydrocarbons plays an important role in the production of value-added chemicals. A key step in this process is the activation of C(sp 3 )-H bond by photogenerated holes. However, the inadequate hole generation and lack of surface adsorption-activation sites severely hinders the improvement in photocatalytic C-H bond oxidation. In particular, the random charge migration to the surface impedes the effective capture of holes by surface active sites to dissociate the C(sp 3 )-H bond. Here, we design and fabricate a Co 3 O 4 /Cs 3 Sb 2 Br 9 p-n heterojunction that effectively addresses these challenges. The p-n heterojunction forms strong built-in electric fields (BEF) facilitating spatial charge separation. Holes are accumulated on Co 3 O 4 , while electrons are accumulated on Cs 3 Sb 2 Br 9 , thereby offering abundant active holes and electrons. Moreover, Co 3 O 4 shows stronger adsorption and activation capacity for the C(sp³)-H bond, enabling the C(sp 3 )-H bond dissociation with low reaction energy barrier. Consequently, the holes are directionally extracted from photoactive Cs 3 Sb 2 Br 9 to catalytically active Co 3 O 4 under visible light irradiation, thereby accelerating the toluene oxidation. The optimized 5 % Co 3 O 4 /Cs 3 Sb 2 Br 9 exhibits a benzyl aldehyde (BAD) evolution rate of 5044 μmol g −1 h −1 and a benzyl alcohol (BA) production rate of 1820 μmol g −1 h −1 , which are 12 and 17 times higher than that of blank Cs 3 Sb 2 Br 9 , respectively.
研究领域:
材料科学
·
化学工程
·
光化学
·
催化
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Yu-Yang Liu,Shan Xu,Xiao-Xin Li,Run-Han Li,Xin-Ting Cai,Hui-Zhen Zhong,Jiang Liu,Qing Huang,Lei Zhang,Shun-Li Li,Ya-Qian Lan
Developing strategies and photocatalysts for C(sp3)-H bond functionalization under simple and mild conditions is important but challenging. Here, we report two redox heterocluster-based frameworks, named Ni5-PW12 and Ni5-V16, in which the terminal oxygen atoms of polyoxometalates are directly coordinated to metal atoms in metal–organic clusters. Due to the coexisting strong oxidation and reduction capacities, both of these photocatalysts achieve photocatalytic C(sp3)-H bond oxidative imination through combining oxidation of methyl aromatics and reduction of nitro aromatics reactions. The experimental and theoretical results reveal that benefiting from the short distance between the clusters, the rapid charge transfer and mass transfer processes would enhance the photocatalytic reactivity and inhibit side reactions. More importantly, all of the photocatalytic reactions are carried out in mild conditions at room temperature without any additional solvents, photosensitizers, oxidizing or reducing agents, or cocatalysts.
研究领域:
光催化
·
有机合成
·
材料化学
·
簇化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Zihao Cui,Qianqian Zhang,Hui Fu,Qihao Liu,Xiaolei Liu,Yaqiang Wu,Peng Gao,Zeyan Wang,Zhaoke Zheng,Hefeng Cheng,Yuanyuan Liu,Ying Dai,Baibiao Huang,Peng Wang
Herein, a facile anti-solvent preparation strategy is proposed to fabricate lead-free halide perovskite Cs 3 Bi 2 Br 9 with TiO 2 , which boosts photocatalytic activation of C(sp 3 )−H bonds in toluene oxidation . TiO 2 not only works as nucleation center to reduce the particle size of perovskite, but could form type II heterojunction with Cs 3 Bi 2 Br 9 , thus improving the photocatalytic performance of the TiO 2 /Cs 3 Bi 2 Br 9 composite. Under AM 1.5 G simulated sunlight irradiation, the optimal TiO 2 /Cs 3 Bi 2 Br 9 composite exhibits both high production rate (9692.5 μmol g −1 h −1 ) and selectivity (91 %) of benzaldehyde product. As verified by in-situ ESR, in-situ FT-IR and DFT calculations, •O 2 − and h + are demonstrated to be the main active species in this process. This work provides a new insight into the design of high-performance lead-free perovskite photocatalysts for organic synthesis.
研究领域:
材料科学
·
光催化
·
有机合成
·
纳米技术
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）