APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Rui Tian,Shiying Fan,Guohua Chen,Xinyong Li
The photocatalytic conversion of methane into valuable liquid oxygenates presents a promising strategy for advancing a sustainable chemical industry. However, achieving both high conversion efficiency and high selectivity using non-precious metal catalysts under ambient conditions remains a significant challenge. Inspired by the functional characteristics of natural enzymatic catalytic systems, this study has constructed a multicomponent synergistic catalytic system with ZnMn₂O₄ as the support. Through the defective engineering design of fluorine doping and in situ growth of tungsten species, it achieves efficient construction of the microenvironment of active centers and precise regulation of free radical intermediates. The optimized 3W20F-ZnMn₂O₄ catalyst achieved a liquid-phase product yield (including methanol and ethanol, etc.) of 442.02 μmol·g⁻¹ ·h⁻¹ with a selectivity of 98.6 % under ambient temperature and pressure—surpassing the performance of most reported non-precious metal-based catalytic systems. Studies have demonstrated that catalysts doped with the two elements exhibit significant differences in the oxygen sources of products, which reflects the distinct pathways they follow in catalyzing methane oxidation. Specifically, the oxygen vacancy (FVo) sites formed by F doping primarily adhere to a single reaction pathway using water as the oxygen source, where the active oxygen species are mainly dominated by ·OH generated from the dissociation of water molecules, ultimately yielding ethanol and small amount of methanol. In contrast, the active sites formed by W doping involve multiple reaction pathways. The production of ethanol relies more on ·OH from water molecule dissociation, while the generation of methanol and methyl hydroperoxide is more dependent on active oxygen species derived from oxygen activation. This study deepens the understanding of the multi-element synergistic catalytic mechanism and lays a foundation for the development of sustainable and efficient catalytic systems.
研究领域:
催化化学
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环境化学
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材料科学
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光催化
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可持续化学
✓ 已验证
产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2025
·
IF 9.2
Yahui Jiang,Haichuan He,Dan Xia,Hongwei Zhang,Shirui Tan,Li Luo,Yifan Kong,Liu Deng,You-Nian Liu
Cu-based catalysts are widely employed in the electrocatalytic CO2 reduction reaction (CO2RR) toward multi-carbon (C2+) products due to their unique electronic structures. However, Cu-based catalysts are prone to reconstruction under working conditions. Self-reduction and undesirable reconstruction have limited the activity and selectivity of these catalysts. Understanding their reconstruction behavior is crucial for elucidating reaction mechanisms and rationally designing catalysts. In this study, Br-doped Cu-base catalysts were employed to investigate the influence of dopants on catalyst surface reconstruction during CO2RR. Characterizations confirmed that during CO2RR, partial Br− leached from the precursor, while residual bromide ions in the Cu matrix created a bromine-rich environment on the catalyst surface, stabilizing Cu0/Cu+ active sites. The reconstructed catalyst exhibited superior selectivity for C2+ products and higher current density. In situ characterization and theoretical calculations demonstrated that the interaction between Br and Cu atoms suppressed complete Cu reduction. Furthermore, the asymmetric coupling pathway via *CO and *CHO intermediates dominated C2+ product formation, with significantly reduced Gibbs free energy of key intermediates compared to undoped CuO. Notably, halogen doping was validated as a universal strategy—Cu–Cl and Cu–F catalysts similarly enhanced C2+ production while exhibiting analogous reconstruction behavior. This study provided deep insights into catalyst surface reconstruction and offered effective strategies for designing high-performance catalysts for CO2RR.
研究领域:
电化学
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催化
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材料科学
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环境化学
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能量转换
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表面科学
✓ 已验证
产品关联
DOI
高影响因子
BIOMACROMOLECULES
·
2024
·
IF 5.5
Danyu Lv,Wanjun He,Wei Liu,Yuqiang Cheng,Yan Cui,Xiujuan Zhou,Yanwen Xue,Siming Yu,Ningjin Zhang,Hecheng Meng,Yongguang Guan,Jian-He Sun,Xian-Ming Shi
The γ-cyclodextrin (γ-CD) metal–organic frameworks (CD-MOF-1) consist of γ-CD and potassium (K+) ions through coordinating an eight-coordinated K+ ion with two C5-linked oxygen and C6-linked hydroxyl (C5–O/C6–OH) groups in the primary faces of adjacent γ-CD units and two C2- and C3-linked hydroxyl (C2–OH/C3–OH) groups in the secondary faces. Herein, we found polysaccharide gels with only C2–OH/C3–OH or C5–O/C6–OH groups in pyranoid rings can form four-coordinated K+ ions and then coordinate γ-CD in a KOH solution for CD-MOF-1 growth. Exposure of C2–OH/C3–OH or C5–O/C6–OH groups in polysaccharide gels is important to form active four-coordinated K+ ions. Mechanism supporting this work is that four-coordinated K+ ion sites are first formed after coordinating C2–OH/C3–OH groups in pectin and then coordinating C5–O/C6–OH groups in the primary faces of γ-CD units. Alternatively, four-coordinated K+ ions with C5–O/C6–OH groups in chitosan can coordinate the C2–OH/C3–OH groups in the secondary faces of γ-CD units. Mechanism of CD-MOF-1 growing on pectin and chitosan gels through the proposed four-coordinated K+ ions is also universally applicable to other polysaccharide gels with similar C2–OH/C3–OH or C5–O/C6–OH groups such as alginate gel. Based on this mechanism, we developed pectin and chitosan gel-based CD-MOF-1 composites and exemplified applications of them in antibacterial and organic dye removal. To help future research and applications of this mechanism, we share our theoretical assumption for further investigations that any matrices with an ortho-hydroxyl carbon chain or ortho-hydroxyl ether structures may form four-coordinated K+ ions for CD-MOF-1 growth. The proposed mechanism will broaden the development of novel CD-MOF-1 composites in various fields.
研究领域:
材料科学
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化学
·
生物材料
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2024
·
IF 5.6
Hongzhen Luo,Tairan Zhou,Rui Zhang,Qianyue Yang,Xinyan You,Shijie Wang,Jiabin Wang,Fang Xie,Rongling Yang
Efficient production of second-generation biofuels (bioethanol and biobutanol) from renewable lignocellulosic biomass holds strategic importance and aligns with sustainability objectives. However, it poses a persistent long-term challenge because of the biomass recalcitrance. Therefore, development of mild, environmentally friendly biomass pretreatment methods is a critical concern. To this end, in this study, a ternary deep eutectic solvent (DES) was synthesized with choline chloride , succinic acid , and glycerol at a molar ratio of 1:0.5:0.5. The ternary DES pretreatment largely enhanced glucan digestibility of corn stover (CS) to 94.7 % which was 4.60-fold to untreated CS. Mechanism of improved enzymatic efficiency of DES-pretreated CS was revealed by characterization methods such as SEM, XRD, and FTIR technologies. In addition, adding 1.0 % H 2 SO 4 to the ternary DES further increased enzymatic hydrolysis yield to nearly 100 %. Subsequently, the H 2 SO 4 -assisted DES-pretreated CS was used as substrate to produce C2-C4 bioalcohols (ethanol and butanol) by microbial fermentations. The results indicate that 46.6–49.2 g/L ethanol could be obtained by S. cerevisiae under separate hydrolysis and fermentation (SHF), and simultaneous saccharification and fermentation (SSF) strategies. Meanwhile, up to 11.9 g/L butanol was achieved from CS hydrolysate by Clostridium acetobutylicum with fed-batch mode. Finally, an artificial microbial consortium by co-culturing C. acetobutylicum and S. cerevisiae was developed which efficiently co-produced 12.4 g/L biobutanol and 5.7 g/L bioethanol from CS hydrolysate. Overall, this study provides a sustainable and green pretreatment technology that deconstruct lignocellulose and possess universality to produce various low-carbon bioalcohols by microbial fermentations.
研究领域:
生物技术
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生物化工
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可再生能源
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环境科学
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微生物学
✓ 已验证
产品关联
DOI
高影响因子
Advanced Science
·
2024
·
IF 14.3
Wu Gu,Huiwen Zhang,Zhichun Zhang,Mingkai Xu,Xiang Li,Zhiyang Han,Xuanhe Fu,Xu Li,Xiujuan Wang,Chenggang Zhang
Staphylococcal Enterotoxin C2 (SEC2), a classical superantigen, is an antitumor immunotherapy agent. However, the injectable formulation of SEC2 limits its clinical application. Here, it is reported that oral administration of SEC2 activates the intestinal immune system and benefits intestinal health in a mouse model. These results indicate that intact SEC2 is detected in the stomach, intestine, and serum after oral administration. Continuous oral administration of SEC2 activates immune cells in gut-associated lymphoid tissues, promoting extensive differentiation and proliferation of CD4 + and CD8 + T cells and CD19 + B cells, leading to increased production of cytokines and secretory immunoglobulin A. SEC2 also enhances intestinal barrier function, as demonstrated by an increased villus length/crypt depth ratio and elevated expression of mucins and tight junction proteins. Additionally, SEC2 indirectly influenced gut microbiota, reinforcing potential probiotics and short-chain fatty acid synthesis. Enhanced differentiation of T and B cells in the spleen, coupled with elevated serum interleukin-2 levels, suggests systemic immune enhancement following oral administration of SEC2. These findings provide a scientific basis for the development of SEC2 as an oral immunostimulant for immune enhancement and anti-tumor immunotherapy.
研究领域:
免疫学
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微生物学
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胃肠病学
·
药理学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH PART B-PESTICIDES FOOD CONTAMINANTS AND AGRICULTURAL WASTES
·
2019
·
IF 1.463
Kai Chen,Mao-Xi Huang,Qing-Cai Shi,Xin Xie,Lin-Hong Jin,Wei-Ming Xu,Xiang-Yang Li
Pheromones can be used as leafhopper attractants. However, commercial pheromone products, such as the Ingle lure, have certain limitations, including poor persistence in the field. In this study, (E)-2-hexenal, (Z)-3-hexen-1-ol, (Z)-3-hexenyl acetate, (E)-ocimene, linalool, and geraniol were selected and behaviorally tested as potential leafhopper attractants. Y-tube olfactometer tests showed that the C2 formulation was more effective than other formulations. In tea field trials, the number of leafhoppers caught by sticky board traps baited with C2 lures was greater than that caught by treatment. The number of leafhoppers attracted by the C2 lures was greater than that attracted by the commercial Ingle lures. Additionally, the total amount of active C2 components on lures was greater than that of the active components on the lure after 14 days. Thus, the results indicated that the C2 formulation may attract leafhoppers and have a greater persistence than other formulations in tea field.
研究领域:
昆虫学
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农业科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2024
·
IF 4.1
Yu Xie,Wangyang Wang,Jiale Cui,Hui Li,Kang Cheng,Qinghong Zhang,Ye Wang
The oxidative coupling of methane (OCM) into C 2−3 hydrocarbons is still limited to a few types of catalysts with low product yield. Herein, we reported our discovery that a K 2 SO 4 -promoted TiO 2 catalyst can effectively catalyze the OCM reactions with a C 2−3 yield of up to 26 %, which is comparable to the classical Mn-NaWO x /SiO 2 catalyst. Besides, this catalyst not only exhibits promising stability for at least 200 h without signs of deactivation under typical OCM conditions but also demonstrates high sulfur-resistance performance, outperforming most reported catalysts. We have evidenced that K + ions are responsible for increasing the surface basicity of rutile TiO 2 , thus benefiting C 2−3 selectivity. The presence of SO 4 2− can prevent the formation of potassium titanates, which catalyze the over-oxidation of CH 4 . The surface lattice oxygen species are confirmed to be the active sites for selective CH 4 activation, while the chemisorbed oxygen species catalyze the combustion of CH 4 to CO 2 .
研究领域:
化学工程
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Yanzhi Xu,Changli Li,Yequan Xiao,Chenghui Wu,Yanming Li,Yanbo Li,Juguang Han,Qinghua Liu,Jingfu He
The combination of Cu and Ag presents a promising way to steer the CO2 reduction products through regulating the surface active sites. However, the difficulty in forming the CuAg alloy with a controllable atomic ratio impedes the in-depth understanding of the structure–activity relationship of CuAg catalysts. Herein, we use E-beam evaporation to synthesize a series of CuAg films with uniform distribution and controllable stoichiometry to reveal the real reaction mechanism on CuAg for the electrochemical CO2 reduction process. Compared with Cu, the Cu1–xAgx (x = 0.05–0.2) alloy showed an apparent suppression of HCOOH and the ratio between C2 liquid products (e.g., ethanol and acetate) and C1 liquid product (HCOOH) is also increased. Operando synchrotron radiation Fourier transform infrared spectroscopy results suggest that the introduction of Ag into the Cu phase can significantly strengthen the absorbed *CO and *OCCO intermediates and suppress the O–C–O intermediates. This research provides a reliable way to inhibit the generation of HCOOH and enhance the production of liquid C2 products during CO2RR and presents a guideline for the future manipulation of copper catalysts by alloying.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Nano
·
2022
·
IF 18.027
Peng Wang,Tan Li,Qiqi Wu,Ruian Du,Qinghua Zhang,Wei-Hsiang Huang,Chi-Liang Chen,Yan Fan,Haonan Chen,Yanyan Jia,Sheng Dai,Yongcai Qiu,Keyou Yan,Yuanyuan Meng,Geoffrey I. N. Waterhouse,Lin Gu,Yun Zhao,Wei-Wei Zhao,Guangxu Chen
In certain metalloenzymes, multimetal centers with appropriate primary/secondary coordination environments allow carbon–carbon coupling reactions to occur efficiently and with high selectivity. This same function is seldom realized in molecular electrocatalysts. Herein we synthesized rod-shaped nanocatalysts with multiple copper centers through the molecular assembly of a triphenylphosphine copper complex (CuPPh). The assembled molecular CuPPh catalyst demonstrated excellent electrochemical CO2 fixation performance in aqueous solution, yielding high-value C2+ hydrocarbons (ethene) and oxygenates (ethanol) as the main products. Using density functional theory (DFT) calculations, in situ X-ray absorption spectroscopy (XAS) and quasi-in situ X-ray photoelectron spectroscopy (XPS), and reaction intermediate capture, we established that the excellent catalytic performance originated from the large number of double copper centers in the rod-shaped assemblies. Cu–Cu distances in the absence of CO2 were as long as 7.9 Å, decreasing substantially after binding CO2 molecules indicating dynamic and cooperative function. The double copper centers were shown to promote carbon–carbon coupling via a CO2 transfer-coupling mechanism involving an oxalate (OOC–COO) intermediate, allowing the efficient production of C2+ products. The assembled CuPPh nanorods showed high activity, excellent stability, and a high Faradaic efficiency (FE) to C2+ products (65.4%), with performance comparable to state-of-the-art copper oxide-based catalysts. To our knowledge, our findings demonstrate that harnessing metalloenzyme-like properties in molecularly assembled catalysts can greatly improve the selectivity of CO2RR, promoting the rational design of improved CO2 reduction catalysts.
研究领域:
化学
·
材料科学
·
环境科学
✓ 已验证
DOI
高影响因子
Marine Drugs
·
2021
·Vol. 19
·期 6
·336
·
IF 5.118
Ni Wu,Mengmeng Tong,Siyu Gou,Weiji Zeng,Zhuoyun Xu,Tianjiu Jiang
Chattonellaspecies,C. marinaandC. ovata, are harmful raphidophycean flagellates known to have hemolytic effects on many marine organisms and resulting in massive ecological damage worldwide. However, knowledge of the toxigenic mechanism of these ichthyotoxic flagellates is still limited. Light was reported to be responsible for the hemolytic activity (HA) ofChattonellaspecies. Therefore, the response of photoprotective, photosynthetic accessory pigments, the photosystem II (PSII) electron transport chain, as well as HA were investigated in non-axenicC. marinaandC. ovatacultures under variable environmental conditions (light, iron and addition of photosynthetic inhibitors). HA and hydrogen peroxide (H2O2) were quantified using erythrocytes and pHPA assay. Results confirmed that% HA ofChattonellawas initiated by light, but was not always elicited during cell division. Exponential growth ofC. marinaandC. ovataunder the light over 100 µmol m−2s−1or iron-sufficient conditions elicited high hemolytic activity. Inhibitors of PSII reduced the HA ofC. marina, but had no effect onC. ovata. The toxicological response indicated that HA inChattonellawas not associated with the photoprotective system, i.e., xanthophyll cycle and regulation of reactive oxygen species, nor the PSII electron transport chain, but most likely occurred during energy transport through the light-harvesting antenna pigments. A positive, highly significant relationship between HA and chlorophyll (chl) biosynthesis pigments, especially chlc2and chla, in both species, indicated that hemolytic toxin may be generated during electron/energy transfer through the chlc2biosynthesis pathway.Keywords:Chattonella marina;Chattonella ovata;hemolytic activity;photosystem II;hydrogen peroxide;chlorophyllc2
研究领域:
生物学
·
生态学
·
毒理学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2022
·
IF 12.92
Zhaopeng Liu,Youming Ni,Zhongpan Hu,Yi Fu,Xudong Fang,Qike Jiang,Zhiyang Chen,Wenliang Zhu,Zhongmin Liu
The utilization of metal oxide-zeolite catalysts in the syngas-to-olefin reaction is a promising strategy for producing C 2 –C 4 olefins from non-petroleum resources. However, the effect of the crystal phase of metal oxides on the catalytic activity of these oxides is still ambiguous. Herein, typical metal oxides (ZnO/ZrO 2 ) with different crystal phases (monoclinic ( m -ZrO 2 ) and tetragonal ( t -ZrO 2 )) were employed for syngas conversion. The (ZnO/ m -ZrO 2 +SAPO-34) composite catalyst exhibited 80.5% selectivity for C 2 –C 4 olefins at a CO conversion of 27.9%, where the results are superior to those (CO conversion of 16.4% and C 2 –C 4 olefin selectivity of 76.1%) obtained over (ZnO/ t -ZrO 2 +SAPO-34). The distinct differences are ascribed to the larger number of hydroxyl groups, Lewis acid sites, and oxygen defects in ZnO/ m -ZrO 2 compared to ZnO/ t -ZrO 2 . These features result in the formation of more formate and methoxy intermediate species on the ZnO/ m -ZrO 2 oxides during syngas conversion, followed by the formation of more light olefins over SAPO-34. The present findings provide useful information for the design of highly efficient ZrO 2 -based catalysts for syngas conversion.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Xuewei Hao,Jiaming Wu,Xintong Cai,Keyan Li,Chunshan Song,Xinwen Guo
The development of photocatalysts for efficient CO 2 conversion to chemicals especially C 2+ products remains a challenge. In this work, Ag nanoparticles (NPs) decorated GaN photocatalysts were synthesized by in-situ nitridation of Ga 2 O 3 combined with chemical deposition of Ag. The photocatalytic performance of Ag/GaN photocatalysts was optimized by tuning the loading amount and ripening time of Ag NPs, among which 0.3Ag/GaN exhibited best photocatalytic CO 2 reduction performance. The production rates of CO and CH 4 reached 421 and 80 μmol g −1 h −1 , respectively, and especially, it also produced C 2 H 6 with a production rate of 79 μmol g −1 h −1 . The introduction of Ag NPs not only significantly promotes visible light absorption as well as charge generation and separation, but also elevates surface temperature of the photocatalyst due to photothermal effect, resulting from localized surface plasmon resonance (LSPR) effect of Ag NPs. Moreover, the addition of Ag NPs enhances the adsorption of both CO 2 and the *CO intermediate, facilitating the CO 2 activation and subsequent C−C coupling process. This study provides new ideas for the design and preparation of photocatalysts capable of converting CO 2 into value-added chemicals.
研究领域:
材料科学
·
催化化学
✓ 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）