ANALYST
·
2022
·Vol. 147
·期 7
·1341-1347
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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
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材料科学
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环境科学
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产品关联
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Jiayuan Sun,Shanshan Shao,Xinggang Hu,Xiaohua Li,Huiyan Zhang
The aqueous fraction of bio-oil from biomass fast pyrolysis mainly contains low-molecular-weight oxygenates such as carboxylic acids, ketones, aldehydes, phenols, and furans. In this study, the full components of aqueous bio-oil are directionally converted into carbonyl groups such as aldehydes and ketones, and then the oxygen-containing precursors of aviation fuel are prepared through coupling, focusing on exploring the mechanism of carbonylation and C–C coupling. Studies have revealed that propionic acid, furfural, and phenol can be directionally converted into ketones, in which reaction 3-pentanone, cyclopentanone, and cyclohexanone were formed via ketonization and hydrogenation in the aqueous phase. Then the two components of 3-pentanone, cyclopentanone, cyclohexanone, acetone, and acetaldehyde were subjected to aldol condensation to explore the C–C coupling mechanism in the preparation of the C7–C18 precursor of aviation fuel. The mechanism in the high-quality utilization of all components of the aqueous phase bio-oil fraction was explored, which was favorable for the synthesis of biomass-based aviation fuel.
研究领域:
化学工程
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可再生能源
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生物质转化
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DOI
高影响因子
ACS Catalysis
·
2022
·
IF 13.7
Xuliang Lin,Xing Fei,Dalang Chen,Yi Qi,Quanzhou Xu,Yinchun Liu,Qian Zhang,Sha Li,Tiejun Wang,Yanlin Qin,Xueqing Qiu
The conversion of renewable bioethanol into high-energy-density higher alcohols has become essential for meeting the increasing global demand to achieve carbon neutrality. In this study, Zn- and nitrogen-codoped Ni-based lignin-derived carbon catalysts (NiZn@NC) were prepared by solvent volatile self-assembly and in situ reductive carbonization using pulp and paper waste stream alkali lignin as the carbon source. Lignin amphipathic derivatives with −COOH and −NH2 groups would coordinate with metal ions to form a stable lignin–metal framework; thus, the lignin-derived carbon layer disperses the NiZn bimetallic catalyst and prevents from corroding. At an amination reagent/lignin mass ratio of 1:2, an ethanol conversion of 75.2% and a high alcohol yield of 41.7% were achieved over the Ni20Zn1@NC catalyst. Experimental results and density functional theory calculations showed that Zn doping improved the electronic environment and defect structures of metallic Ni and carbon carrier, which effectively inhibited C–C cleavage and suppressed the byproduct formation, such as methane. Thereby, the synergetic effect between Ni and Zn facilitated the efficient conversion of aqueous ethanol into higher alcohols by the Guerbet reaction. This work provides a strategy of in situ pyrolytic doping and stabilizing of renewable biomass macromolecules as the frameworks for the construction of highly active and cost-efficient catalysts for ethanol upgrading.
研究领域:
催化化学
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可再生资源利用
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材料科学
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DOI
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
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环境科学
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能源科学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2025
·
IF 4.8
Jianhao Li,Zhicheng Hu,Shuhuan Han,Dapeng Cao,Xiaofei Zeng,Jianfeng Chen
Electrocatalytic CO 2 reduction reaction (CO 2 RR) to multi-carbon product, especially for ethylene (C 2 H 4 ), provides a favorable pathway for carbon neutrality and renewable energy storage. However, the second-order C-C coupling reactions in CO 2 RR need always the high activation/driven energy in dynamics originating from the trace C 1 intermediate product. Herein, we synthesized the Ag-decorated Cu 2 O porous hollow core-shell catalyst named Ag@Cu 2 O where Ag nanoparticles uniformly distributed on inner the surface of the hollow Cu 2 O (H-Cu 2 O) via the sacrificial template method. Benefiting from the synergistic hollow structure and electron transfer from Cu and Ag to O, Ag@Cu 2 O catalyst delivers the excellent C 2 H 4 Faradaic Efficiency (FE) of 55 % ± 2 % at −1.0 V (vs. RHE), which is superior to the most reported catalysts. More importantly, in situ infrared spectroscopy and density functional theory (DFT) calculations reveal the introduction of Ag can decrease the activation energy required for *CO and C-C coupling.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-11
·
IF 14.7
Yang Ruixin,Cai Yanming,Qi Yongbing,Tang Zhuodong,Zhu Jun-Jie,Li Jinxiang,Zhu Wenlei,Chen Zixuan
C–C coupling is of utmost importance in the electrocatalytic reduction of CO 2 , as it governs the selectivity of diverse product formation. Nevertheless, the difficulties to directly observe C–C coupling pathways at a specific nanocavity hinder the advances in catalysts and electrolyzer design for efficient high-value hydrocarbon production. Here we develop a nano-confined Raman technology to elucidate the influence of the local electric field on the evolution of C–C coupling intermediates. Through precise adjustments to the Debye length in nanocavities of a copper catalyst, the overlapping of electrical double layers drives a transition in the C–C coupling pathway at a specific nanocavity from *CHO–*CO coupling to the direct dimerization of *CO species. Experimental evidence and simulations validate that a reduced potential drop across the compact layer promotes a higher yield of CO and promotes the direct dimerization of *CO species. Our findings provide insights for the development of highly selective catalyst materials tailored to promote specific products.
研究领域:
催化化学
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电化学
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产品关联
DOI
PubMed
高影响因子
ACS Catalysis
·
2023
·
IF 12.9
Shunan Zhang,Chaojie Huang,Zilong Shao,Haozhi Zhou,Junjun Chen,Lin Li,Junwen Lu,Xiaofang Liu,Hu Luo,Lin Xia,Hui Wang,Yuhan Sun
Revealing and regulating the intricate reaction mechanism of direct CO2 hydrogenation to higher alcohols (C2+OH), especially for the crucial C–C coupling step, is still a great challenge. Herein, the specific reaction network on Co2C and CuZnAl multifunctional tandem catalysts is elucidated by designing subtly surface adsorption–desorption reactions, in situ chemical transient kinetics, and theory calculations. The key C–C coupling step for the formation of C2+OH over the sole Co2C catalyst was the insertion of CO into R-CHx, while the reaction mechanism can be modulated to the coupling of R-CH2 and CHO with a lower energy barrier on the tandem catalyst (Co2C||CuZnAl). R-CH2 was derived from the hydrogenation dissociation of olefins and coupled with the CHO from formate hydrogenation at the Cu/ZnAl2O4 interface. Such multifunctional tandem catalysts exhibited a high space–time yield of C2+OH of 2.2 mmol g–1 h–1. This work provides an effective strategy for studying complex mechanisms, contributing to the precise design of highly efficient catalysts and the optimization of reaction pathways.
研究领域:
催化化学
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理论计算
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能源化学
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产品关联
DOI
高影响因子
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
·
2023
·Vol. 120
·期 44
·e2307320120
·
IF 11.1
Yangyang Yu,Ye He,Ping Yan,Shengyao Wang,Fan Dong
The selective photocatalytic conversion of CO2 and H2O to high value-added C2H4 remains a great challenge, mainly attributed to the difficulties in C–C coupling of reaction intermediates and desorption of C2H4* intermediates from the catalyst surface. These two key issues can be simultaneously overcome by alloying Ag with Cu which gives enhanced activity to both reactions. Herein, we developed a facile stepwise photodeposition strategy to load Cu–Ag alloy sub-nanoclusters (ASNCs) on TiO2 for CO2 photoreduction to produce C2H4. The optimized catalyst exhibits a record-high C2H4 formation rate (1110.6 ± 82.5 μmol g−1 h−1) with selectivity of 49.1 ± 1.9%, which is an order-of-magnitude enhancement relative to current work for C2H4 photosynthesis. The in situ FT-IR spectra combined with DFT calculations reveal the synergistic effect of Cu and Ag in Cu–Ag ASNCs, which enable an excellent C–C coupling capability like Ag and promoted C2H4* desorption property like Cu, thus advancing the selective and efficient production of C2H4. The present work provides a deeper understanding on cluster chemistry and C–C coupling mechanism for CO2 reduction on ASNCs and develops a feasible strategy for photoreduction CO2 to C2 fuels or industrial feedstocks.
研究领域:
化学
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材料科学
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环境科学
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产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Huimin Li,Zhe Sun,Chenlong Dong,Xueli Zhang,Chengkun Lei,Baobao Jin,Qianqian Shen,Husheng Jia,Jinbo Xue
Photocatalytic non-oxidative coupling of methane is an attractive strategy for CH 4 to C 2 conversion, how to facilitate the photogenerated charge separation and accelerate the C–C coupling to promote the reaction kinetics remains a great challenge. Herein, a symbiotic r-Fe 2 O 3 /NiO heterostructure with robust interfaces is constructed in situ. The coherent interface not only provides unique Ni–O–Fe asymmetric sites, but also achieves the separation and transport of photogenerated charge. The unbalanced charge density distribution of two adjacent methyl or methylene at the Ni–O–Fe asymmetric site alleviates the dipole repulsion of the C–C coupling, and promotes C–C coupling to form C 2 hydrocarbons. Under visible light irradiation, the optimal r-Fe 2 O 3 /NiO performs a brilliant C 2 activity up to 71.00 μmol g −1 h −1 , and the C 2 H 4 yield can reach a high value of 40.46 μmol g −1 h −1 and the selectivity of 56.98 %. This work provides new insights into the coupling of C–C to generate C 2 hydrocarbons.
研究领域:
材料科学
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化学工程
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产品关联
DOI
高影响因子
DALTON TRANSACTIONS
·
2024
·Vol. 53
·期 26
·10919-10927
·
IF 3.5
Xuanzhao Lu,Baozhen Yuan,Yi Liu,Li-Xia Liu,Jun-Jie Zhu
Electrochemical reduction of carbon dioxide (CO2) or carbon monoxide (CO) to valuable multi-carbon (C2+) products like acetate is a promising approach for a sustainable energy economy. However, it is still challenging to achieve high activity and selectivity for acetate production, especially in neutral electrolytes. Herein, a bioinspired hemin/Cu hybrid catalyst was developed to enhance the surface *CO coverage for highly efficient electroreduction of CO to acetate fuels. The hemin/Cu electrocatalyst exhibits a remarkable faradaic efficiency of 45.2% for CO-to-acetate electroreduction and a high acetate partial current density of 152.3 mA cm−2. Furthermore, the developed hybrid catalyst can operate stably at 200 mA cm−2 for 14.6 hours, producing concentrated acetate aqueous solutions (0.235 M, 2.1 wt%). The results of in situ Raman spectroscopy and theoretical calculations proved that the Fe–N4 structure of hemin could enhance the CO adsorption and enrich the local concentration of CO, thereby improving C–C coupling for acetate production. In addition, compared to the unmodified Cu catalysts, the Cu catalysts functionalized with cobalt phthalocyanine with a Co–N4 structure also exhibit improved acetate performance, proving the universality of this bioinspired molecule-enhanced strategy. This work paves a new way to designing bioinspired electrolysis systems for producing specific C2+ products from CO2 or CO electroreduction.
研究领域:
电化学
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催化材料
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能源化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CATALYSIS TODAY
·
2020
·
IF 5.825
Lijie Zhang,Mei Li,Shengbo Zhang,Xuerui Cao,Jinxiao Bo,Xinli Zhu,Jinyu Han,Qingfeng Ge,Hua Wang
Electrochemical CO 2 reduction (CO 2 RR) to ethanol is a way to advance CO 2 utilization toward a renewable chemical feedstock and fuel. In present study, an approach to promote ethanol production is employed through adding Au, which is favorable toward CO formation, onto Cu 2 O catalysts. Namely, the Cu 2 O hollow nanospheres with a size of 150−180 nm were synthesized by a soft template method, and then Au nanoparticles of ∼7 nm were loaded to obtain Au x /Cu 2 O composites. The Au x /Cu 2 O catalysts have an earlier onset for ethanol production than Cu 2 O. Besides, Au x /Cu 2 O catalysts display the significantly enhanced Faraday efficiencies (FEs) of CO and ethanol, the suppressed hydrogen evolution reaction and the slightly weakened HCOOH formation. Among them, Au 0.17 /Cu 2 O stands out with the highest FEs of ethanol from 10.8%–16.2% throughout the measuring potentials, suggesting an optimal amount of Au. Furthermore, it is found that the FEs of ethanol increase as the atomic ratio of Au/Cu increases at the medium reduction potentials (-1.1 V to -1.3 V). Besides, it is demonstrated that ethanol formation is more favorable over ethylene formation, evidenced by the ratio of FE ethanol /FE ethylene reaching 2.0, 3.3, 4.1 on three Au x /Cu 2 O catalysts, respectively. This correlation between the ethanol production and the Au amount reflects that Au plays a crucial role in promoting ethanol formation. The enhanced ethanol formation is ascribed to more CO formation on Au sites to promote C–C coupling. Our study demonstrates an effective approach to develop Cu-based electrocatalysts for ethanol formation from CO 2 .
研究领域:
化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Zhizhou Cai,Ning Cao,Fanxing Zhang,Xiangzhou Lv,Ke Wang,Yi He,Yao Shi,Hao Bin Wu,Pengfei Xie
Electrocatalytic CO 2 reduction into ethanol driven by renewable energy represents a promising strategy for energy storage and mitigation of global warming, but it has remained challenging to gain high activity and selectivity of ethanol. Here we take advantage of atomic arrangement in immiscible Ag-Cu composite during annealing and establish hierarchical interfaces in the obtained core-shell catalyst. The atomic Ag-Cu interactions increase electrochemical surface area and expedite charge dynamics, resulting in an unprecedented electrocatalytic performance with the faradaic efficiency of C 2+ products, ethanol as 80.2 %, 52.6 % and the current density of ∼320 mA cm −2 at −1.0 V (versus reversible hydrogen electrode). Moreover, the Ag-Cu catalyst exhibits a notable stability for ∼60 h. Mechanism studies reveal that local CO intermediates preferentially accumulate on the core, then migrate to the continuous Cu surface for C-C coupling energy-favorably toward ethanol. Our work highlights a novel design principle as interface engineering for advanced tandem electrocatalysts.
研究领域:
材料科学
·
电化学
·
能源存储与转换
✓ 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）