Small
·
2025
·
IF 12.1
Zipei Cui,Yipeng Nie,Longquan Deng,Zhuo Li,Shuo Chen,Wenchao Sheng
Promoting C─C bond cleavage of ethanol to achieve a complete 12-electron pathway (C1 pathway) for ethanol oxidation reaction (EOR) is crucial for the development of highly efficient direct ethanol fuel cells. In this study, a highly porous ultrathin PdSn nanomesh (NM) with high proportion of low-coordinated edge and step sites is developed for alkaline EOR. The PdSn NM/C catalyst exhibited superior specific activity of 21.9 ± 0.9 mA cm −2 Pd with a significantly enhanced Faradaic efficiency of C1 pathway to CO 2 . In situ attenuated total reflection surface enhanced infrared absorption spectroscopy measurements demonstrated the significant enhancement of C1 selectivity on PdSn NM/C. Theoretical calculations further revealed the pivotal role of low-coordinated edge and step sites in effectively lowering the activation energy barrier for C─C bond cleavage of CH 3 CO*. This work provides a strategy for the rational design of highly efficient EOR electrocatalysts through low-coordinated site engineering.
研究领域:
电催化
·
材料科学
·
能量转换
·
纳米材料
·
燃料电池
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Dan Li,Zuquan Gan,Cailin Zhang,Xiuqiu Wang,Mingzhen Zheng,Xiaoyun Gao,Yue Huang,Youjun Fan,Shuifeng Zhang,Fuqin Zheng,Wei Chen
The exploration of sustainable approaches for plastic waste disposal has emerged as an urgent imperative task. This research presents an innovative and eco-friendly electrochemical route to degrade plastic waste, ethylene glycol (EG), into value-added formate. To this end, an interesting hollow FeOOH/CoOOH heterostructure is successfully fabricated for EG oxidation. The difference in work functions between FeOOH and CoOOH results in the establishment of a built-in electric field (BEF), which is beneficial for the adsorption of EG and *OH. As a result, the FeOOH/CoOOH demonstrates outstanding catalytic performance in the EG oxidation reaction (EGOR) with an exceptionally low potential of only 1.32 V at 10 mA cm -2 and a high Faraday efficiency of 92.19% for formate generation. Glycollic acid is identified as a pivotal intermediate in the EGOR by in-situ infrared spectroscopy. Theoretical computations disclose that the FeOOH/CoOOH heterostructure not only causes an upward shift of the d-band center but also largely enhances the *OH adsorption, thus speeding up the cleavage of the inert C-C bond and markedly facilitating the conversion of EG to formate. This research not only enriches the fundamental comprehension of the EGOR but also provides deep insights for the rational design of highly selective and active EGOR catalysts.
研究领域:
电化学
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催化
·
材料科学
·
环境科学
·
纳米技术
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Rui Zhai,Zhenyu Wang,Chang Huang,Chao Zeng,Mengyue Gu,Tianqi Wang,Fanqi Bu,Shaobin Wang,Jinying Zhang
Phosphorus has various crystallographic structures and variable phosphorus-derived structures, which have attracted much attention due to its unique properties. One-dimensional phosphorus structures with atomic substitution in the phosphorus lattice are extremely favored due to their high specific surface area and stable single-atom dispersion. The precise crystal structures and single atomic substitution positions are crucial factors to understand the mechanism of single-atom effects but remain a big challenge. Herein, single crystals composed of 1D zigzag linear phosphorus selenium chains (ZLP-Se) have been produced and characterized by SC-XRD to be P18.56Se1.44 with a space group of Pnma (CSD-2348033). The exact Se substitution positions were further ascertained by calculations of the whole thermodynamic stability phase diagram to have three types of substitution patterns (Se1/P1 mixed occupied positions with intervals of 3Se+2P, 1Se+4P, and 1Se+1P+1Se+2P). The selenium-rich crystal plane (-10-1) has been demonstrated to significantly enhance CO2 adsorption and C−C coupling to obtain ethylene (C2H4). A high photocatalytic CO2 reduction performance (18.0 μmol g−1 h−1, 97.0% electron selectivity for C2H4) has been achieved by the ZLP-Se with the Ag cocatalyst. The adsorption of CO2* and CO* was found to be much stronger on the Se-rich surface of ZLP-Se. The CO* intermediates were found to be energetically favored for protonation and subsequent asymmetrical C−C coupling to produce C2H4, with COCHO* intermediates detected by in situ DRIFTS. The electron was also demonstrated by in situ XPS to transfer from Se and Ag to P under Xe lamp irradiation, confirming the electronic localization effect of ZLP-Se to yield C2H4.
研究领域:
材料科学
·
催化
·
物理化学
·
纳米技术
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2025
·
IF 17.7
Xianlong Lu,Lili Wang,Xueyang Zhao,Binbin Pan,Zhendong Li,Xiangfei Du,Shihan Zhang,Fan Dong,Bangwei Deng
Copper (Cu)-based catalysts show significant potential for producing high value-added C 2+ products in electrocatalytic CO 2 /CO reduction reactions (CO (2) RR). However, the structural reconfiguration during operation poses substantial challenges in identifying the intrinsic catalytic active site, especially under similar mass transport conditions. Herein, three typical and commercial Cu-based catalysts (Cu, CuO, and Cu 2 O) are chosen as representatives to elucidate the structure-activity relationship of CORR in the membrane electrode assembly electrolyzer. Notably, only the Cu catalyst demonstrates the most suppression of hydrogen evolution reaction, thus achieving the highest FE of 86.7% for C 2+ products at a current density of 500 mA cm –2 and maintaining a stable electrolysis over 110 h at a current of 200 mA cm –2 . The influence of chemical valence state of Cu, electrochemical surface area, and local pH were firstly investigated and ruled out for the significant FE differences. Finally, based on the structure analysis from high resolution transmission electron microscope, OH – adsorption, in situ infrared spectroscopy and density functional theory calculations, it is suggested that the asymmetric C-C coupling ( via *CHO and *CO) is the most probable reaction pathway for forming C 2+ products, with Cu (100)-dominant grain boundaries (GBs) being the most favorable active sites. These findings provide deeper insights into the synergistic relationship between crystal facets and GBs in electrocatalytic systems.
研究领域:
电化学
·
催化
·
材料科学
·
纳米技术
·
物理化学
✓ 已验证
产品关联
DOI
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2023
·
IF 11.4
Yingying Zhou,Jia-jia Jiao,Huang Huang,Yong Dong Liu,Rugang Zhong,Xin Yang
Dichloroacetonitrile (DCAN) as one of the potentially prioritized regulated DBPs has drawn great attention; however, understanding its formation, especially the C–C bond cleavage mechanisms, is limited. In this study, DCAN formation mechanisms from long-chain primary amines, amino acids, and dipeptides during chlorination were investigated by a combined computational and experimental approach. The results indicate that nitriles initially generate for all of the above precursors, then they undergo β-C-hydroxylation or/and α-C-chlorination processes, and finally, DCAN is produced through the Cα–Cβ bond cleavage. For the first time, the underlying mechanism of the C–C bond cleavage was unraveled to be electron transfer from the O– anion into its attached C atom in the chlorinated nitriles, leading to the strongly polarized Cα–Cβ bond heterocleavage and DCAN– formation. Moreover, DCAN molar yields of precursors studied in the present work were found to be determined by their groups at the γ-site of the amino group, where the carbonyl group including −CO2–, −COR, and −CONHR, the aromatic group, and the −OH group can all dramatically facilitate DCAN formation by skipping over or promoting the time-consuming β-C-hydroxylation process and featuring relatively lower activation free energies in the C–C bond cleavage. Importantly, 4-amino-2-hydroxybutyric acid was revealed to possess the highest DCAN yield among all the known aliphatic long-chain precursors to date during chlorination. Additionally, enonitriles, (chloro-)isocyanates, and nitriles can be generated during DCAN formation and should be of concern due to their high toxicities.
研究领域:
环境化学
·
水处理
·
毒理学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ANALYTICAL CHEMISTRY
·
2024
·
IF 6.7
Yuling Li,Jiahui Bai,Kuofeng Tseng,Xiaoqiang Zhang,Li Zhang,Jing Zhang,Wenjian Sun,Yinlong Guo
Free unsaturated fatty acids (UFA) are key intermediates of lipid metabolism and participate in many metabolic pathways with specific biological functions. Although various fragmentation-based methods for pinpointing C═C locations in UFA were developed, the current mass spectrometry methods are difficult to simultaneously differentiate geometric isomers and positional isomers in trace samples due to low ionization efficiency, low conversion, and low resolution. Herein, an intramolecular ring–chain equilibrium elimination strategy via 4-plex stable isotope labeling dual derivatization-assisted ion mobility-mass spectrometry was developed, thereby one-pot specifically labeling C═C and carboxyl groups among the trace and unstable UFA with high sensitivity, high efficiency, and good substrate generality. It achieved fast separation of both C═C positional and geometric isomers with high resolution, which benefited from eliminating the intramolecular ring–chain equilibrium by suppressing the formation of salt bridges between free carboxyl groups and pyridine cations. 4-plex stable isotope labeling reagents showed similar reactivity, enabling high-throughput quantitative analysis of omics. This method was successfully applied for accurate and rapid identification of the UFA composition in olive oil extract. These results suggest that the developed method provides new insight for rapid characterization of UFA C═C positional and geometric isomers in complex samples to explore disease biomarkers and food quality control indicators.
研究领域:
分析化学
·
脂质组学
·
质谱分析
·
代谢组学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Energy Chemistry
·
2024
·
IF 14
Xiaoyue Zhang,Yong Yang,Yingjie Hu,Lijun Xiong,Tianyu Wang,Panjie Li,Jinyou Shen
Photothermal catalytic CO 2 conversion provides an effective solution targeting carbon neutrality by synergistic utilization of photon and heat. However, the C–C coupling initiated by photothermal catalysis is still a big challenge. Herein, a three-dimensional (3D) hierarchical W 18 O 49 /WTe 2 hollow nanosphere is constructed through in-situ embodying of oxygen vacancy and tellurium on the scaffold of WO 3 . The light absorption towards near-infrared spectral region and CO 2 adsorption are enhanced by the formation of half-metal WTe 2 and the unique hierarchical hollow architecture. Combining with the generation of oxygen vacancy with strengthened CO 2 capture, the photothermal effect on the samples can be sufficiently exploited for activating the CO 2 molecules. In particular, the close contact between W 18 O 49 and WTe 2 largely promotes the photoinduced charge separation and mass transfer, and thus the *CHO intermediate formation and fixedness are facilitated. As a result, the C–C coupling can be evoked between tungsten and tellurium atoms on WTe 2 . The ethylene production by optimized W 18 O 49 /WTe 2 reaches 147.6 μmol g − 1 with the selectivity of 80%. The in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations are performed to unveil the presence and significance of aldehyde intermediate groups in C–C coupling. The half-metallic WTe 2 cocatalyst proposes a new approach for efficient CO 2 conversion with solar energy, and may especially create a new platform for the generation of multi-carbon products.
研究领域:
材料科学
·
催化
·
化学工程
·
环境科学
·
纳米技术
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2018
·
IF 4.908
Yang Zhou,Lu Li,Lijun Jin,Jian Zhou,Zhiwei Shi,Yang Li,Haoquan Hu
Coal pyrolysis is generally considered to initiate by cleavage of weak covalent bonds bridged between aromatic rings. The C–C covalent bonds are predominant bridged linkages among the framework of coal, which have a critical influence on coal pyrolysis reaction but lack of direct online observation. Five representative coal-related model compounds containing C–C bridged bonds, polypropylene (PP), polyvinylpyrrolidone (PVP), poly-4-vinylpyridine (P4VP), polystyrene (PS) and poly-4-vinylphenol, were selected to pyrolyze in an in-situ pyrolysis vacuum ultraviolet photoionization mass spectrometry (Py-VUV-PIMS). The soft ionized mass spectral detection can provide product distribution and evolved information of original products and intermediates, which are the key evidence to understand the initiation, recombination and reaction routes during pyrolysis process. Online analysis of pyrolysis reaction was found to be priority with cracking of C–C bond in the five polymer samples, and homologous free radicals and original products, which mainly include monomers, dimers and their alkyl and alkenyl radicals, were detected. The results reveal the cleavage temperature of C–C covalent bond is deeply related to its chemical environment, and obvious conjugation effect and steric effect for the bridged linkage were observed. In addition, the effect of hydrogen bond was also observed during the pyrolysis of model compounds containing hydroxyl groups, and intramolecular or intermolecular hydrogen bonding reduced the temperature at which C–C bridged bonds break. The analogous fracture mode and pyrolysis behavior of coal-related model compounds, which are beneficial to understand the reaction route and mechanism of coal pyrolysis, were discussed based on the experimental observations and theoretical calculation.
研究领域:
化学工程
·
分析化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Bioengineered
·
2022
·
IF 6.832
Yuanmei Che,Jianglong He,Xiaopeng Li,Daxian Wu,Yi Zhang,Guicai Yuan
microRNAs, as small endogenous RNAs, influence umpteen sophisticated cellular biological functions regarding neurodegenerative and cerebrovascular diseases. Here, we interrogated miR-381-3p’s influence on BV2 activation and neurotoxicity in ischemic and hypoxic environment. Oxygen-glucose deprivation (OGD) was adopted to induce microglial activation and HT-22 neuron damage. Quantitative polymerase chain reaction (qRT-PCR) was taken to check miR-381-3p expression in OGD-elicited BV2 cells and HT-22 neurons. It transpired that miR-381-3p expression was lowered in BV2 cells and HT-22 cells elicited by OGD. miR-381-3p up-regulation remarkably hampered inflammatory mediator expression in BV2 cells induced by OGD and weakened HT22 neuron apoptosis. In vivo, miR-381-3p expression was abated in HI rats’ ischemic lesions, and miR-381-3p up-regulation could ameliorate inflammation and neuron apoptosis in their brain. C-C chemokine receptor type 2 (CCR2) was identified as the downstream target of miR-381-3p, and miR-381-3p suppressed the CCR2/NF-κB pathway to mitigate microglial activation and neurotoxicity. Therefore, we believed that miR-381-3p overexpression exerts anti-inflammation and anti-apoptosis in ischemic brain injury by targeting CCR2
研究领域:
神经科学
·
分子生物学
·
神经退行性疾病
·
脑血管疾病
✓ 已验证
DOI
PubMed
高影响因子
FUEL
·
2024
·
IF 6.7
Zhuang Li,Zi-Chun Fan,Xiang Bai,Xian-Yong Wei,Yierxiati. Dilixiati,Qian-Qian Kong,Ji Zhao,Yong-Hui Feng,Jun-Long Wang,Xing Fan,Xiao-Yan He,Hai-Xu Zou,Zhi-Min Zong
MY zeolites with mesopores were prepared by hydrothermal method using functionalized SiO 2 (F-SiO 2 ) as a silica source, and hydrophobic bifunctional Ru/MY- O catalysts were obtained by deposition precipitation method and silylation treatment. This work aims at obtaining polycyclic alkane (PCA) based high-density hydrocarbon fuels (HDHFs). We focused on the catalytic hydroconversion (CHC) of 2-phenoxy-1-phenylethanol (PP-ol) and oxydibenzene (ODB), two typical lignin-related model compounds (LRMCs), over Ru/MY- O . The effects of different reaction conditions and catalysts on the product distribution in PP-ol and ODB were investigated. The partial hydrogenation of ODB was found to be a necessary step before achieving C-O ether bond cleavage and C-C bond coupling. The balance of metal/acidic sites is critical for maximizing PCA yields. Changes in the metal/acid ratio had a greater effect on PCA yield in PP-ol than in ODB. Poor stability of cycloalkyl cations and partial hydrogenation of ODB hinder the generation of C-C coupling products. The incorporation of mesopores and hydrophobic treatment were found to weaken the negative effects of C-C bond coupling products and water on the catalyst. The conversion of Ru 3 /MY- O was improved by nearly 10% compared to Ru 3 /Y in the fifth cycle reaction. This work provided a theoretical basis for the generation of HDHFs from lignin.
研究领域:
化学工程
·
催化
·
可再生能源
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2022
·Vol. 13
·期 1
·50
·
IF 4.501
Yifan Zheng,Lin Gu,Yining Li,Jamal Ftouni,Abhishek Dutta Chowdhury
The quest for improved heterogeneous catalysts often leads to sophisticated solutions, which are expensive and tricky to scale up industrially. Herein, the effort to upgrade the existing inorganic nonmetallic materials has seldom been prioritized by the catalysis community, which could deliver cost-effective solutions to upgrade the industrial catalysts catalog. With this philosophy in mind, we demonstrate in this work that alloyed palladium-lead (Pd-Pb) deposited on novel precipitated calcium carbonate (PCC) supports could be considered an upgraded version of the industrial Lindlar catalyst for the semi-hydrogenation of phenylacetylene to styrene. By utilizing PCC supports of variable surface areas (up to 60 m2/g) and alloyed Pd-Pb loading, supported by material characterization tools, we showcase that achieving the “active-site isolation” feature could be the most pivotal criterion to maximize semi-hydrogenated alkenes selectivity at the expense of prohibiting the complete hydrogenation to alkanes. The calcite phase of our PCC supports governs the ultimate catalysis, via complexation with uniformly distributed alloyed Pb, which may facilitate the desired “active-site isolation” feature to boost the selectivity to the preferential product. Through this work, we also advocate increasing research efforts on mineral-based inorganic nonmetallic materials to deliver novel and improved cost-effective catalytic systems.Keywords:heterogeneous catalysis;hydrogenation;alloyed catalyst;calcium carbonate;functionalization of C-C/C-H bonds
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
PLoS One
·
2013
·Vol. 8
·期 3
·e59882
·
IF 3.73
Lushan Yu,Yan Jiang,Lu Wang,Rong Sheng,Yongzhou Hu,Su Zeng
BYZX, [(E)-2-(4-((diethylamino)methyl)benzylidene)-5,6-dimethoxy-2,3-dihydroinden-one], belongs to a series of novel acetylcholinesterase inhibitors and has been synthesized as a new chemical entity for the treatment of Alzheimer’s disease symptoms. When incubated with human liver microsomes (HLMs), BYZX was rapidly transformed into its metabolites M1, M2, and M3. The chemical structures of these metabolites were identified using liquid chromatography tandem mass spectrometry and nuclear magnetic resonance, which indicated that M1 was an N -desethylated and C = C hydrogenation metabolite of BYZX. M2 and M3 were 2 precursor metabolites, which resulted from the hydrogenation and desethylation of BYZX, respectively. Further studies with chemical inhibitors and human recombinant cytochrome P450s (CYPs), and correlation studies were performed. The results indicated that the N -desethylation of BYZX and M2 was mediated by CYP3A4 and CYP2C8. The reduced form of β-nicotinamide adenine dinucleotide 2′-phosphate was involved in the hydrogenation of BYZX and M3, and this reaction occurred in the HLMs and in the human liver cytosol. The hydrogenation reaction was not inhibited by any chemical inhibitors of CYPs, but it was significantly inhibited by some substrates of α,β-ketoalkene C = C reductases and their inhibitors such as benzylideneacetone, dicoumarol, and indomethacin. Our results suggest that α,β-ketoalkene C = C reductases may play a role in the hydrogenation reaction, but this issue requires further clarification.
研究领域:
药理学
·
生物化学
·
阿尔茨海默病研究
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）