APPLIED CATALYSIS B-ENVIRONMENTAL
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2023
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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
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光催化
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有机合成
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纳米技术
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产品关联
DOI
高影响因子
Biochar
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2023
·Vol. 5
·期 1
·1-18
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IF 12.7
Wang Shulian,Huang Yan,Ma Shuanglong,Zhan Sihui,Wang Jingzhen,Gao Boqiang,Tang Xiaodan,Zhu Qiuhui,Xu Shengjun,Zhuang Xuliang
Metal-free porous biochars are popularly utilized as catalysts for peroxydisulfate (PDS) activation. The enhancement effect of PDS activation of porous biochars fabricated by employing both hard template and alkali metal activating agent has not been explored completely. In addition, the role of the inherent carbon defect in PDS activation has not been clearly elucidated. Hence, a series of carbonaceous catalysts were fabricated using a sole template (KCl), a sole activating agent (Na 2 S 2 O 3 ) or a combination of template and activating agent (KCl/Na 2 S 2 O 3 , KCl/KHCO 3 , KCl/NaHCO 3 , and KCl/Na 2 C 2 O 4 ), to systematically investigate the effect of specific surface area (SSA) and intrinsic defect of porous biochar on its PDS activation ability. The biochar synthesized by KCl and Na 2 S 2 O 3 (SK-C) exhibited the optimum degradation performance. The SK-C was found to possess an interconnected hollow cage with three-dimensional mesh structure showing the largest surface area, pore volume and C- sp 3 edge defect content among all the catalysts, which explained its paramount catalytic ability. The SSA and C- sp 3 content together can determine the catalytic performance in a quantitative relationship. The single electron transfer pathway from SDZ to inner-sphere bound SK-C/PDS* was the protagonist of pollutant oxidation. The degradation intermediates were detected and recognized and their toxicities were evaluated. This study for the first time comprehensively identified the synergistic effect between the SSA and inherent defects on improving the catalytic performance of biochar for PDS activation to removal contaminants. Graphical Abstract
研究领域:
环境科学
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材料科学
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化学工程
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水处理
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产品关联
DOI
高影响因子
Molecular Catalysis
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2023
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IF 4.6
Xiangquan Qin,Yiping Jiang,Jie Chen,Fuquan Yao,Longyi Jin,Zhiqi Cong
Selective hydroxylation of C( sp 3 )–H bonds is a long-standing challenge in the organic synthesis field. We herein report an artificial P450 peroxygenase system facilitated by ω-pyridyl fatty acyl amino acids that can hydroxylate broad-spectrum alkanes, including linear and cyclic alkanes and benzylic and allylic alkane chains. Compared with the previously reported dual-functional small molecule (DFSM) with imidazole as a catalytic group (Im-DFSM), pyridyl DFSM (Pyd-DFSM) produced substantially higher total turnover numbers (TTNs) for the hydroxylation of medium-chain alkanes and cycloalkanes (C6–C8), e.g., 12.0-fold and 17.1-fold increased TTNs of P450 mutant F87A/T268V for heptane and cycloheptane , respectively. In addition, Pyd-DFSM altered the enantioselectivity of benzylic hydroxylation, e.g., it almost inverted the configuration observed in the benzylic hydroxylation of ethylbenzene and tetralin . More importantly, Pyd-DFSM showed excellent regioselectivity for allylic hydroxylation over epoxidation of terminal alkenes and cycloalkenes , e.g., up to 94% allylic hydroxylation of 1-hexene was observed. This work significantly enhances the catalytic toolbox of the DFSM-facilitated P450 peroxygenase system; it not only substantially expands the chemical space of P450 enzymes, but also provides an alternative solution for the selective hydroxylation of C( sp 3 )–H bonds.
研究领域:
有机化学
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生物化学
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催化
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酶工程
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DOI
高影响因子
Science China-Chemistry
·
2021
·Vol. 64
·期 5
·770-777
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IF 9.445
Qiao Xiaofeng,Lin Yuhan,Li Jiazhen,Ma Wanhong,Zhao Jincai
Both β- and γ- hydroxyketone structures are important units in biologically active molecules, synthetic drugs and fine chemicals. Although there are some routes available for their manufacture from pre-functionalized groups on one or two matrix molecule(s), the approaches to simply and simultaneously deposit two oxygen atoms from dioxygen into two specific C(sp 3 ) positions of pure saturated hydrocarbons have rarely succeeded because they are involved in the targeted activation of three inert C-H σ bonds all at once. Here, we show that a TiO 2 -CH 3 CN photocatalytic suspension system enables the insertion of dioxygen into one C(sp 3 )-C(sp 3 ) bond of strained cycloparaffin derivatives, by which difunctionalized hydroxyketone products are obtained in a one-pot reaction. With the cleavage event to release strain as the directional driving force, as-designed photocatalytic reaction systems show 21 examples of β-hydroxyketone products with 31%–76% isolated yields for three-membered ring derivatives and 5 examples of γ-hydroxyketone products with 30%–63% isolated yields for four-membered ring substrates. 18 O isotopic labeling experiments using 18 O 2 , Ti 18 O 2 and intentionally added H 2 18 O, respectively, indicated that both oxygen atoms of hydroxyketone products were exclusively from dioxygen, suggesting a previously unknown H + /TiO 2 -e − catalyzed arrangement pathway of the hydroperoxide intermediate to convert dioxygen into hydroxyketone units.
研究领域:
有机化学
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光催化化学
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药物化学
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DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
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2017
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IF 4.849
Jian Cheng,Jun Sun,Jiekuan Yan,Song Yang,Pengcheng Zheng,Zhichao Jin,Yonggui Robin Chi
The metal-free catalytic functionalization of aromatic sp2-carbons and benzylic sp3-carbons remains challenging. Here we report a carbene-catalyzed functionalization of the 3-methyl sp3-carbon attached to 2-formyl-indoles. The reaction proceeds through an NHC-bound o-quinodimethane as the key intermediate generated from 2-formyl-3-methylindoles under oxidative conditions. Reactive ketones are found to be effective substrates to produce substituted hydropyrano[3,4-b]indoles in good to excellent yields.
研究领域:
有机化学
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合成化学
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DOI
高影响因子
Journal of Materials Chemistry A
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2022
·Vol. 10
·期 20
·11268-11276
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IF 14.511
Jiabao Guo,Yizhuo Zhao,Peng Wang,Yang Song,Yifei Shao,Li Zhu,Xiaoquan Yao
Catalytic selective cleavage reaction of the C(sp3)–C(sp3) bond has received little attention, despite its importance in organic synthesis and biochemistry. Herein, a novel copper loaded nitrogen-rich mesoporous carbon nitride material was designed and synthesized, and utilized as a highly efficient photocatalyst for the inert C–C bond cleavage of amines under blue light irradiation. With oxygen as a benign oxidant, good to excellent yields were achieved for various functionalized amines at room temperature, even including sluggish aliphatic amines. The method may provide a cost-effective and environmentally friendly alternative for the direct oxidative cleavage of amines.
研究领域:
有机合成
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光催化化学
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材料科学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2022
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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
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化学工程
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光化学
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DOI
高影响因子
Materials Horizons
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2025
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IF 10.7
Jian-Hui Zheng,Chang-Long Tan,Ming-Yu Qi,Zi-Rong Tang,Yi-Jun Xu
Harnessing the power of photoredox catalysis for the selective C(sp3)−H activation and oxidation of alkyl aromatics represents a cutting-edge approach to transforming petroleum-derived feedstocks into value-added C(sp3)−C(sp3) coupled chemicals. Herein, we delve into the photocatalytic process that involves the selective dehydrocoupling of ethylbenzene (EB) to access 2,3-diphenylbutane (DPB) alongside H2, employing three sulfur source-varied ZnIn2S4 (denoted as ZIS-x) catalysts. ZIS-TAA, with thioacetamide (TAA) as sulfur source, exhibits exceptional photocatalytic efficiency for DPB and H2 production. The results show the deficiency of charge carrier recombination centers in defect-poor ZIS-TAA is conducive to the separation of photogenerated charge. Additionally, the larger specific surface area and more surface functional groups provide abundant sites for reactant adsorption and activation, facilitating redox process aided by an ideal band-edge structure. This work illustrates a simple and cost-effective paradigm for designing semiconductor-based photocatalysts with tailored surface properties to enhance the efficiency of target cooperative photoredox reaction.
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产品关联
DOI
PubMed
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2020
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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
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环境科学
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催化化学
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DOI
高影响因子
iScience
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2023
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IF 5.8
Cheng Wang,Zirui Qiao,Yulan Tian,Haijun Yang,Huaqiang Cao,Anthony K. Cheetham
Imines are important intermediates for synthesizing various fine chemicals, with the disadvantage of requiring the use of expensive metal-containing catalysts. We report that the dehydrogenative cross-coupling of phenylmethanol and benzylamine (or aniline) directly forms the corresponding imine with a yield of up to 98%, and water as the sole by-product, in the presence of a stoichiometric base, using carbon nanostructures as the “green” metal-free carbon catalysts with high spin concentrations, which is synthesized by C(sp 2 )-C(sp 3 ) free radical coupling reactions. The catalytic mechanism is attributed to the unpaired electrons of carbon catalysts to reduce O 2 to O 2 ·− , which triggers the oxidative coupling reaction to form imines, whereas the holes in the carbon catalysts receive electrons from the amine to restore the spin states. This is supported by density functional theory calculations. This work will open up an avenue for synthesizing carbon catalysts and offer great potential for industrial applications.
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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DOI
高影响因子
ACS Catalysis
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2026
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IF 13.6
Jun-Bin He,Lian Wu,Wenli Yuan,Hai-Xue Pan,Binju Wang,Gong-Li Tang
Achieving highly regioselective C–H bond functionalization at the bridgehead carbon of a single molecule is a fascinating, yet formidable challenge. BcmD, a P450 enzyme, catalyzes the regioselective hydroxylation at the sp3-hybridized bridgehead carbon of the bicyclo[4.2.2]piperazinedione ring scaffold during bicyclomycin biosynthesis. Herein, we provide mechanistic details of BcmD to understand its substrate binding and the origin of its regioselectivity. The high-resolution structure of SoBcmD from Streptomyces ossamyceticus in complex with its natural substrate, together with site-directed mutagenesis and computational simulations, reveals that the precise substrate positioning, enabled by specific hydrogen-bonding and hydrophobic interactions with crucial residues, determines the regioselectivity. Intriguingly, we identify SoBcmD as a peroxygenase that could utilize H2O2 as an oxidant to catalyze regioselective hydroxylation. Mechanistic analysis indicates that H2O2 activation in SoBcmD involves a homolytic cleavage process, mediated by a hydrogen-bonding network comprising residues T277, A273, and the substrate. Furthermore, structure-based channel analysis and mutagenesis demonstrate that the I157V mutant exhibits significantly enhanced peroxygenase activity. These findings advance our understanding of regioselectivity control in BcmD and provide valuable guidance for engineering P450 peroxygenases for the C–H bond activation at the chemically challenging bridgehead carbon sites.
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DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
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2025
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IF 3.6
Qiujie Shan,Lu-Lu Chai,David James Young,Zhi-Gang Ren,Hong-Xi Li
The light-promoted, nickel-catalyzed hydrogen-evolution C(sp3)–H acylation of simple alkanes with aromatic aldehydes has been achieved without the need for additional photosensitizers or oxidants. This reliable and atom-economical reaction afforded a broad range of aryl alkyl ketones in good yields, with H2 as the sole byproduct. It was successfully demonstrated on a gram scale as well as for the postfunctionalization of drug molecules. Aromatic aldehydes play multiple roles, including a photosensitizer, a coupling partner, and a hydrogen atom transfer agent.
研究领域:
有机化学
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催化化学
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光化学
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绿色化学
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药物化学
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合成化学
✓ 已验证
DOI
PubMed
高影响因子
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