INORGANIC CHEMISTRY
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2024
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IF 4.3
Qinxuan Cao,Jianning Feng,Jinzhong Zhang,Jie Xue,Kang Wang,Ye Yang,Haipeng Lu
Direct utilization of solar energy by semiconductor nanocrystals for chemical transformations via photocatalysis has recently drawn a great deal of attention. While most photocatalytic reactions are mediated through photoredox events, the ultimate reaction scalability relies on the use of sacrificial agents. The imbalanced population of photogenerated electrons and holes often leads to catalyst degradation through photocorrosion. To circumvent this, we designed Ni2+-doped CsPbBr3 nanoplatelets (NPls) as a “redox-neutral” photocatalyst, where both oxidative and reductive cycles occur in one photocatalyst. We showed that surface Ni2+ ions can act as an “electron shuttle” to reduce protons, generating clean-energy H2 gas, while the photogenerated holes can be used to oxidize diaryl hydrazines to afford valuable azobenzenes and derivatives. Compared with previous photocatalytic demonstrations, our catalysts show excellent reaction yields with a wide substrate scope, unity atomic efficiency, and enhanced stability and recyclability.
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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催化
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产品关联
DOI
PubMed
高影响因子
Nature Nanotechnology
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2024
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IF 38.1
Zhang Gong,Li Yongqi,Zhao Chenxuan,Gu Jiabao,Zhou Gang,Shi Yanfeng,Zhou Qi,Xiao Feng,Fu Wen-jie,Chen Qingbai,Ji Qinghua,Qu Jiuhui,Liu Huijuan
Industrial hypersaline wastewaters contain diverse pollutants that harm the environment. Recovering clean water, alkali and acid from these wastewaters can promote circular economy and environmental protection. However, current electrochemical and advanced oxidation processes, which rely on hydroxyl radicals to degrade organic compounds, are inefficient and energy intensive. Here we report a flow-through redox-neutral electrochemical reactor (FRER) that effectively removes organic contaminants from hypersaline wastewaters via the chlorination–dehalogenation–hydroxylation route involving radical–radical cross-coupling. Bench-scale experiments demonstrate that the FRER achieves over 75% removal of total organic carbon across various compounds, and it maintains decontamination performance for over 360 h and continuously treats real hypersaline wastewaters for two months without corrosion. Integrating the FRER with electrodialysis reduces operating costs by 63.3% and CO 2 emissions by 82.6% when compared with traditional multi-effect evaporation-crystallization techniques, placing our system at technology readiness levels of 7–8. The desalinated water, high-purity NaOH (>95%) and acid produced offset industrial production activities and thus support global sustainable development objectives.
研究领域:
环境工程
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废水处理
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电化学
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可持续性
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DOI
PubMed
高影响因子
Nature Communications
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2017
·Vol. 8
·期 1
·1-7
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IF 12.124
Lin Jin,Li Zhi,Kan Jian,Huang Shijun,Su Weiping,Li Yadong
Catalytic oxidative C–H bond functionalization reactions that proceed without requiring stoichiometric amounts of external oxidants or pre-functionalized oxidizing reagents could maximize the atom- and step-economy in chemical syntheses. However, such a transformation remains elusive. Here, we report that a photo-driven catalytic process enables decarboxylative C–H trifluoromethylation of (hetero)arenes with trifluoroacetic acid as a trifluoromethyl source in good yields in the presence of an external oxidant in far lower than stoichiometric amounts (for example, 0.2 equivalents of Na 2 S 2 O 8 ) using Rh-modified TiO 2 nanoparticles as a photocatalyst, in which H 2 release is an important driving force for the reaction. Our findings not only provide an approach to accessing valuable decarboxylative C–H trifluoromethylations via activation of abundant but inert trifluoroacetic acid towards oxidative decarboxylation and trifluoromethyl radical formation, but also demonstrate that a photo-driven catalytic process is a promising way to achieve external oxidant-free C–H functionalization reactions.
研究领域:
有机化学
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催化
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光化学
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DOI
PubMed
高影响因子
Nature Communications
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2025
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IF 15.7
Na Qi,Zhang Xiaowang,Long Linna,Qi Siyu,Zhang Zhiyu,Zhi Ruoyu,Tan Zhuotao,Ying Hanjie,Zhu Chenjie
The textile dyeing industry has shaped modern aesthetics through vibrant coloration technologies. Indigoid dyes embody this potential but are hindered by the hazardous chemo-synthesis and water-intensive chemo-dyeing processes. While biosynthesis and bio-dyeing efforts offer alternatives, disjointed synthesis-dyeing steps lead to unsustainable water and energy demands, and complex biosynthetic pathways cause low atom economy and inefficiency. Here, we report a one-pot one-step approach that unifies biosynthesis and bio-dyeing of indigoids to drastically reduce water usage in the dyeing process. By combining alcohol dehydrogenase with flavin-containing monooxygenase, we construct an artificial redox-neutral cascade biosynthetic pathway to produce bluish-violet indigoid dyes, which significantly enhances atom economy and achieves high production efficiency. Various natural and synthetic fabrics are dyed in-situ with the biosynthetic indigoids utilizing recombinant E. coli whole cells. Crucially, this system dyes synthetic nylon fibers with the historic purple hue.
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DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
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2025
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IF 7.3
Xinqi Xu,Shumin Wang,Yaqun Zhong,Juanjuan Yang,Lian Xu,Bingmei Su,Juan Lin
Whole-cell redox-neutral cascade reactions are promising for the sustainable synthesis of bulky lactones. In this study, the cyclohexanone monooxygenase from Acinetobacter sp. NCIMB 9871 (CHMOAc) was rationally designed based on enhancing product release and consensus sequence design to enhance the activity and stability of the enzyme. A four-point mutant MU4 (G14A/A43G/M400L/F432I) showed improved activity and stability for the oxidation of cyclohexanone to ε-caprolactone at a high substrate loading. A newly NADPH-dependent alcohol dehydrogenase from Pseudomonas monteilii (PmADH) with high cyclohexanol oxidation activity was introduced for constructing the redox-neutral cascade for the synthesis of ε-caprolactone from cyclohexanol. To improve the intracellular environment for cascade synthesis of ε-caprolactone, CRISPR/Cas9-mediated strong promoter insertion to the endogenous catalase gene katE in the NADP self-sufficient Escherichia coli strain BK-1 (Ptrc-nadK/Ptrc-pncB) was done for mitigating the oxidative stress to obtain the strain E. coli BKE-3 harboring MU4 and PmADH. Finally, 776 mM cyclohexanol could be converted into ε-caprolactone by the BKE-3 whole-cell catalytic system with a >99% conversion rate without cyclohexanone accumulation, which was the highest record for the redox-neutral cascade synthesis of ε-caprolactone. The BKE-3 whole-cell catalytic system also showed high efficiency for the synthesis of various lactones. This work provides an efficient redox-neutral catalytic platform for the sustainable synthesis of lactones featuring high substrate loading and atomic economy.
研究领域:
生物催化
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酶工程
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合成生物学
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生物过程工程
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蛋白质工程
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代谢工程
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工业生物技术
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DOI
高影响因子
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