INORGANIC CHEMISTRY
·
2023
·
IF 4.6
Shanshan Wu,Meng Tian,Yang Hu,Nan Zhang,Wei Shen,Jianyi Li,Linchuan Guo,Pengfei Da,Pinxian Xi,Chun-Hua Yan
Formate is identified as economically viable chemical fuel from electrochemical carbon dioxide reduction. However, the selectivity of current catalysts toward formate is limited by the competitive reaction such as HER. Herein, we propose a CeO2 modification strategy to improve the selectivity of catalysts for formate through tuning of the *OCHO intermediate, which is important for formate production.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2023
·
IF 3.6
Fenfen Xie,Fen Han,Yunying Yan,Haiqiong Li,Jianjun Hao,Linhai Jing,Pan Han
It is significant to develop novel difluoromethylation methods because of the important roles of difluoromethyl groups in the medicinal chemistry and material industries. Here, we developed a novel difluoromethylation–carboxylation and difluoromethylation–deuteration method triggered by a difluoromethyl radical generated by electroreduction of stable and easily available difluoromethyltriphenylphosphonium bromide. Various molecules containing difluoromethyl and carboxyl or deuterium groups can be synthesized through this method. The establishment of this method will provide an alternative to radical difluoromethylation reactions.
研究领域:
有机化学
·
药物化学
✓ 已验证
DOI
PubMed
高影响因子
Nanomaterials
·
2018
·Vol. 8
·期 4
·192
·
IF 3.504
Yifan Zheng,Nana Chen,Chunxiao Wang,Xiaoping Zhang,Zongjian Liu
While high-aspect-ratio metal nanowires are essential for producing nanowire-based electrodes of good performance used in electronics and electrocatalysis, the synthesis of millimeter-long Cu nanowires remains a challenge. This work demonstrates an oleylamine-mediated hydrothermal method for synthesis of Cu nanowires with an average diameter of ~80 nm and a length up to several millimeters. An investigation on the role of oleylamine in nanowire formation by mass spectroscopy, small angle X-ray diffraction and transmission electron microscopy reveals that oleylamine serves as a mild reducing agent for slow reduction of Cu(II) to Cu, a complexing agent to form Cu(II)-oleylamine complex for guiding the nanowire growth, as well as a surfactant to generate lamellar phase structure for the formation of nanowire bundles. The growth mechanism of these millimeter-long Cu nanowire bundles is proposed based on the experimental observations. Electrochemical measurements by linear sweep voltammetry indicate that the self-supported nanowire electrode prepared from as-formed Cu nanowire bundles shows high catalytic activity for electroreduction of nitrate in water.Keywords:Cu nanowires;hydrothermal method;oleylamine;nitrate;electroreduction
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
ACS Catalysis
·
2019
·
IF 12.221
Yan Liu,Xiangdong Kong,Xu Guo,Qiuyao Li,Jingwen Ke,Ruyang Wang,Qunxiang Li,Zhigang Geng,Jie Zeng
Electroreduction of N2 into NH3 represents a promising method for N2 fixation. However, due to the inertness of N≡N covalent triple bonds, this process remains a huge challenge to achieve a high yield rate of NH3. In this work, we designed an effective approach to promoting N2 activation by introducing oxygen vacancies into LaCoO3. In N2 electroreduction, LaCoO3 with oxygen vacancies (denoted as Vo-LaCoO3) exhibited a Faradaic efficiency of 7.6% for NH3 at −0.6 V versus the reversible hydrogen electrode (RHE). Notably, at −0.7 V versus RHE, the yield rate for NH3 of Vo-LaCoO3 reached 182.2 μgNH3 mg–1cat. h–1, which was 2.8 times higher than that (65.3 μgNH3 mg–1 h–1) of pristine LaCoO3. To the best of our knowledge, the yield rate for NH3 of Vo-LaCoO3 approaches the activities of the state-of-the-art catalysts toward N2 electroreduction. Density functional theory calculations revealed that enhanced activation of N2 over Vo-LaCoO3 originated from the increased charge density around the valence band edge via the introduction of oxygen vacancies. Furthermore, the analysis of the thermodynamic limiting potentials for N2 reduction and H2 evolution demonstrated the higher selectivity for N2 electroreduction over Vo-LaCoO3 relative to pristine LaCoO3.
研究领域:
材料科学
·
催化化学
✓ 已验证
DOI
高影响因子
ACS Catalysis
·
2023
·
IF 12.9
Qian Zhang,Mingzi Sun,Chen-Yue Yuan,Qi-Wen Sun,Bolong Huang,Hao Dong,Ya-Wen Zhang
Constructing abundant surface/interface structures has significant impacts on improving the performance of electrochemical CO2 reduction reaction (CO2RR) catalysts. For developing high-performance CO2RR catalysts, herein we report a 0D/2D heterojunction structure of SnO2 nanodots (∼2 nm) confined on graphitic carbon nitride (g-C3N4) nanosheets for promoting the conversion of CO2 to formate. Experimental and theoretical studies demonstrate that the abundant N-coordinating sites of g-C3N4 and highly distributed SnO2 nanodots synergistically lead to strong metal oxide–support interactions, and the substantial heterojunction interface in SnO2/g-C3N4 has induced efficient electron transfer from electron-rich g-C3N4 to SnO2 mainly through p–p orbital couplings. As a result, the SnO2/g-C3N4 heterojunction provides superior activity and stability for the conversion of CO2RR to formate, with a Faradic efficiency of 91.7% at −0.88 V vs RHE. Moreover, the proposed 0D/2D heterojunction strategy was extended to In2O3/g-C3N4, supplying a universal strategy to achieve efficient hybrid catalysts for CO2RR in the production of high-value chemicals.
研究领域:
材料科学
·
电化学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
ANALYST
·
2022
·Vol. 147
·期 7
·1341-1347
·
IF 5.227
Chen-Chen Jiang,Xiao-Chong Li,Jian-Ang Fan,Jia-Ying Fu,Xu-Nan Huang-Fu,Jia-Jie Li,Ju-Fang Zheng,Xiao-Shun Zhou,Ya-Hao Wang
The electroreductive cleavage of carbon–halogen bonds has attracted increasing attention in both electrosynthesis and pollution remediation. Herein, by employing the in situ electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) technique, we have successfully investigated the electroreductive dehalogenation process of aryl halides with the thiol group on a smooth Au electrode in aqueous solution at different pH values. The obtained potential-dependent Raman spectra directly reveal a mixture of the reduction products 4,4′-biphenyldithiol (BPDT) and thiophenol (TP). The conversion ratios of the C–Cl and C–Br bonds at pH = 7 are 37% and 55%, respectively. Furthermore, quantitative analysis of the intensity variations of ν(C–Cl), ν(C–Br) and aromatic ν(CC) stretching modes suggests electroreductive dehalogenation via both direct electron transfer reduction and electrocatalytic hydrodehalogenation. Molecular evidence for the C–C cross coupling process through TP reaction with benzene free radical intermediates is found at negative potentials, which leads to the increasing selectivity of biphenyl products.
研究领域:
电化学
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Rui Zhang,Feifei Chen,Haokun Jin,Yong Zhang,Xiaoya Hao,Yingda Liu,Tianming Feng,Xinghua Zhang,Zunming Lu,Weihua Wang,Feng Lu,Hong Dong,Hui Liu,Hui Liu,Yahui Cheng
In Cu-based electrocatalysts, appropriate amount of Cu 0 and high concentration of Cu + are essential for the efficient conversion of CO 2 into C 2+ products. An obstacle of CO 2 electroreduction is the inevitable reduction of Cu + to Cu 0 at cathodic potential. Intermediates confinement is a promising solution to delay Cu + deterioration, in which it is crucial to maintain an appropriate amount of Cu 0 and Cu + species to produce sufficient intermediates to protect most Cu + species. Herein, based on the influence of Cu + /Cu 0 ratio on the reaction process and its feedback, a series of hollow Cu 2 O nanoreactors with different cavity sizes were synthesized to modulate the concentration of intermediates and the coverage degree of Cu + , so as to realize a constant high Cu + /Cu 0 ratio. The optimized hollow Cu 2 O nanoreactors achieved a C 2+ Faradaic efficiency of 70.1 ± 0.2 % at a partial current density of −9.3 ± 0.1 mA cm −2 over 30 h and a large C 2+ -to-C 1 ratio of 9.73. Operando Raman spectra and quasi in - situ Auger electron spectra confirmed that the moderate cavity Cu 2 O nanoreactors led to a full coverage of Cu + and an optimal Cu + /Cu 0 ratio of 8.12:1, which brought the stability of Cu + species and cavity structure, as well as the enhanced C C dimerization.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
iScience
·
2023
·
IF 5.8
Ying Zhang,Yuying Wan,Xiaoxu Liu,Kai Chen,Ke Chu
Electrocatalytic reduction of nitrite to ammonia (NO 2 RR) is considered as an appealing route to simultaneously achieve sustainable ammonia production and abate hazardous nitrite pollution. Herein, atomically Nb-doped NiO nanoflowers are designed as a high-performance NO 2 RR catalyst, which exhibits the highest NH 3 -Faradaic efficiency of 92.4% with an NH 3 yield rate of 200.5 μmol h -1 cm -2 at -0.6 V RHE. Theoretical calculations unravel that Nb dopants can act as Lewis acid sites to render effective NO 2 - activation, decreased protonation energy barriers, and restricted hydrogen evolution, ultimately leading to a high NO 2 RR selectivity and activity.
研究领域:
材料科学
·
环境科学
·
催化化学
✓ 已验证
DOI
PubMed
高影响因子
VACUUM
·
2024
·
IF 3.8
Xiu Wen,Zhixiu Yang,Lijing Gao,Ruiping Wei,Xiaomei Pan,Jin Zhang,Guomin Xiao
Electrocatalytic reduction of CO 2 affords a potential way to mitigate the greenhouse effect and fuel crisis. In this work, we compared highly-dispersed CuO nanocomposites and Cu–Cu 2 O nanocomposites which all derived from Cu x Al-LDH for CO 2 electrochemical reduction . The Cu–Cu 2 O based nanocomposites obtained through the restoration strategies still retain its layered structure, simultaneously increasing dual Cu–Cu 2 O active sites, which exhibit excellent performance in selective reduction of CO 2 to C 2 H 4 . The Cu 5 Al-ER obtained through in-situ electrochemical reduction is modified by bulk phase, which can regulate active species, increase surface active sites, enhance C–C coupling. Meanwhile, the electrochemical strategy offers numerous benefits, including gentle conditions, adjustable monitoring, exceptional efficiency and adaptability. We have confirmed that cost-effective Cu–Cu 2 O based nanocomposite derived from Cu 5 Al-LDH can effectively promote C–C coupling during electrochemical CO 2 conversion and improve FE C2H4 . The FE C2H4 of Cu 5 Al-ER reaches 36% at −1.2 V vs. RHE. And the current density reaches −172 mA·cm −2 at −1.6 V vs. RHE. The results showed that compared to Cu 5 Al-LDO, the FE C2H4 of Cu 5 Al-ER increased by 2.6 times. In addition, Cu 5 Al-ER exhibits excellent stability during the 12 hours CO 2 catalytic reduction process.
研究领域:
化学
·
环境科学
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2024
·
IF 11.3
Xiaofeng Liu,Yuanyuan Sun,Hao Ren,Yan Lin,Mingbo Wu,Zhongtao Li
Electrochemically driven carbon–carbon coupling utilizing renewable electricity under ambient conditions has emerged as an innovative approach for synthesizing high-value chemicals, which still faces inherent challenges such as low conversion rates and poor selectivity. While electroreducing furfural to hydrofuroin can produce high-quality biofuel, its efficiency need to be promoted. Herein, Cu–Sn bimetallic catalyst has been developed with a conversion rate of furfural of >97% and hydrofuroin selectivity of >67% through equilibrium of the interfacial intermediate *H and *fur-CHOH, which exhibits the greatest state-of-the-art overall performance. Characterization and theoretical calculation reveal that Cu serves as the active site for generating *fur-CHOH, whose electron density can be decreased by introducing Sn, and results in a higher *fur-CHOH coverage and a lower energy barrier of dimerization. Moreover, adding Sn also enables sluggish *H formation to balance interfacial *fur-CHOH and *H, leading to reduced hydrogenation byproducts. The as-developed approach provides valuable insights for optimizing other C–C electrocoupling reactions for the synthesis of high-value chemicals.
研究领域:
化学
·
材料科学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
Chem Catalysis
·
2024
·
IF 11.5
Bihua Hu,Bingxian Chu,Hailin Cao,Zhiwei Lei,Shuyu Cui,Peizhi Wang,Jun Tang,Xingzhu Wang,Baomin Xu
Molecular catalysts with precisely designed structures and abundant metal-nitrogen active sites have garnered significant attention for their ability to efficiently perform electroreduction of carbon dioxide (ERCD). However, the catalytic efficiency and selectivity are significantly limited by the fixed electronic structure of the metal-nitrogen structure, resulting in low production efficiency of more valuable products. This work presents the electronic regulation of cobalt phthalocyanine (CoPc) through in situ oxidation of N-doped Ti 3 C 2 T x nanosheets (CoPc/o–N–MXene). The resulting material exhibits high activity and tailorable selectivity. The study confirmed a strong interaction between Co-N 4 active sites and N–MXene after oxidation, resulting in a “Co–N–MXene” bond. This bond contributes to the transformation of intermediate ∗ CO into ∗ HCO, leading to a high selectivity of ERCD to methanol. This work provides a perspective on the mechanism of ERCD to methanol and an avenue for the synthesis of effective catalysts.
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
RSC Advances
·
2015
·Vol. 5
·期 114
·94008-94015
·
IF 3.84
Fen Guo,Ke Ye,Xiaomei Huang,Yinyi Gao,Kui Cheng,Guiling Wang,Dianxue Cao
A novel Pd/polyaniline/CFC electrode is prepared by electroless deposition of palladium (Pd) onto three-dimensional polyaniline networks. The polyaniline matrix on the carbon fiber cloth (CFC) in the reduction state is electro-synthesized by cyclic voltammetry and has a lower vertex potential of −0.4 V vs. Ag/AgCl. The particle size of the Pd coated on the polyaniline chains is gradiently distributed. The as-prepared Pd/polyaniline/CFC electrode is characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FITR) and X-ray diffraction (XRD). The hydrogen peroxide (H2O2) electro-reduction reaction in H2SO4 solutions on the Pd/polyaniline/CFC electrode is investigated using cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). The results reveal that the electrode exhibited high catalytic activity and excellent stability in the strong oxidizing solution of H2O2 and H2SO4. Polyaniline itself shows electro-catalytic activity towards H2O2 to some extent involving the chemical–electrochemical (C–E) coupling mechanism.
研究领域:
材料科学
·
电化学
✓ 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）