Journal of CO2 Utilization
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2018
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IF 5.503
Jianyang Wang,Anfeng Zhang,Xiao Jiang,Chunshan Song,Xinwen Guo
Although many researchers have reported CO 2 hydrogenation to various C1 chemicals, it is still challenging to directly and selectively convert CO 2 to C 2 -C 4 hydrocarbons in terms of overcoming the extreme inertness of CO 2 and a high C C coupling barrier. In the present work, we report an efficient integration of methanol-synthesis and the methanol-to-hydrocarbons with the bifunctional catalyst component of In 2 O 3 -ZrO 2 and SAPO-5. These tandem reactions exhibit an excellent relative selectivity of C 2 -C 4 (83%) with a suppressed CH 4 relative selectivity less than 3% at T = 300 °C. A detailed analysis indicates that the partially reduced indium oxide surface (In 2 O 3 -ZrO 2 ) can better activate CO 2 and promote the synthesis of methanol than In 2 O 3 alone, and C C coupling is subsequently manipulated within the confined acidic pores of SAPO-5 according to XRD, H 2 -TPR, CO 2 -TPD, SEM and TEM. Furthermore, the proximity of two components and the content of Si also play an important role in such outstanding selectivity to C 2 -C 4 . Our study paves a new path for the direct synthesis of lower hydrocarbons.
研究领域:
化学工程
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催化化学
·
能源化学
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2021
·
IF 8.271
Yan-Cheng Hu,Ying Li,Ding-Wei Ji,Heng Liu,Hao Zheng,Gong Zhang,Qing-An Chen
C2 prenylated indoles are widespread in a variety of bioactive natural alkaloids. Therefore, the selective installation of prenyl group at C2 position of NH indoles is of great significance. However, the known protocols generally require a multi-step procedure and stoichiometric promoters. Herein we develop a one-step C2 prenylation of NH indole with cheap tert- prenyl alcohol enabled by acid catalysis. Salient features include good regioselectivity, step- and atom-economy, broad substrate scope, and simple catalytic system. The mechanistic investigations demonstrate that both C2 prenylation and C3 prenylation/migration pathways are engaged in the reaction. Notably, this practical strategy can be applied to the late-stage diversification of tryptophan-based peptides and concise synthesis of tryprostatin B.
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CHINESE JOURNAL OF CATALYSIS
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2024
·
IF 15.7
Changpo Ma,Ying Lai,Tiange Zhao,Xiaoxuan Zhang,Haichao Liu,Weiran Yang
α,ω-Dicarboxylic acids are important intermediates for the preparation of polyamides , polyesters and polyurethanes . However, their production pathways are limited and usually suffer from low efficiency and environmental problems. Here, we report an innovative approach to synthesize C+2 dicarboxylic acids directly from cyclic ethers by dicarbonylation. Different from the general findings that C+1 monocarboxylic acids are produced by carbonylation of cyclic ethers involving alkene intermediates, in this work, by manipulating the reaction system with RhCl 3 and iodine in acetic acid, diiodide-substituted intermediates were selectively formed and subsequently converted to dicarboxylic acids in the presence of H 2 and CO. As high as 84% yield of adipic acid was obtained directly from tetrahydrofuran. This catalytic system is applicable not only to a wide variety of cyclic ethers but also to different primary diols to synthesize C2-elongated α,ω-dicarboxylic acids. This work provides a novel dicarbonylation strategy for the efficient synthesis of adipic acid, glutaric acid and other important α,ω-dicarboxylic acids (such as 1,7-heptanedioic acid and 1,8-octanedioic acid) that are still not easily synthesized by other methods.
研究领域:
有机化学
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催化
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材料科学
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高影响因子
TETRAHEDRON-ASYMMETRY
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2014
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IF 2.165
An-lin Zhang,Li-wen Yang,Nian-fa Yang,Yan-ling Liu
A series of C 2 -symmetric chiral amino diol tridentate ligands 3a – g were prepared from achiral bulky organolithiums, achiral bulky primary amines , and optically active epichlorohydrin (ECH). The prepared C 2 -symmetric chiral amino diol tridentate ligands were capable of inducing enantioselectivity in the model reaction of aromatic and aliphatic aldehydes with diethylzinc with an ee of up to 96%. The enantioselectivity can be modulated by adjusting the steric hindrance of the achiral reagents employed in the synthesis of the chiral ligand. The configuration of the addition product depended on the configuration of the amino diol ligands, which can be simply controlled as desired by using the ECH with the desired configuration during the preparation of the ligand.
研究领域:
有机化学
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催化
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立体化学
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高影响因子
Journal of Materials Chemistry A
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2025
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IF 9.5
Jie Meng,Ying Wang,Li-Yang Shao,Tian-Shu He,Jiao-Na Yue,Bo-Lin Sun,Quan-Guo Zhai
The rational control of heterostructure motifs and the corresponding electronic environment in heterocatalysts offers an effective strategy to regulate CO2RR selectivity, yet it remains challenging. The precise regulation of the reaction intermediates is therefore a critical determinant. In this work, the size-engineered cMOF/o-Cu2O was introduced to modulate heterostructure motifs, thereby modulating the *CHO intermediate selectivity switch and steering C2 or C1 reaction pathways. We elucidated the divergent CO2RR pathways governed by the differential growth degrees of the cMOF/o-Cu2O heterostructures. The minimized cMOF/o-Cu2O-s (∼361.8 nm), comprising a high proportion of –OH terminations, accelerated the continuous hydrogenation of *CHO and promoted their conversion into *CHxO intermediates. The moderate cMOF/o-Cu2O-m (∼870.1 nm) achieved an optimal balance between the intermediate concentrations and interfacial transfer, enabling a preferential *CHO–*CO coupling pathway through the rationally designed heterostructure motifs. In contrast, the enlarged cMOF/o-Cu2O-l (∼2.7 µm) exhibited an indistinguishable force toward the key intermediates of *CHO, thereby failing to differentiate between the subsequent reaction pathways. The intensified *CHxO and *CHO–*CO signals observed in the in situ ATR-FTIR further verified the bifurcated reaction pathways, featuring a C1-dominated pathway on cMOF/o-Cu2O-s and C2 pathway on cMOF/o-Cu2O-m. cMOF/o-Cu2O-m achieved a Faraday efficiency of 71.1% for C2 products at −1.3 V vs. RHE. This work offers crucial insights into the significance of size engineering in modulating the heterostructure motifs to regulate the selectivity switch of key intermediates.
研究领域:
电催化
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材料化学
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二氧化碳还原反应（CO2RR）
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纳米材料工程
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多相催化
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Journal of Physical Chemistry C
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2023
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IF 3.7
Yuanjiao Liu,Yi Wang,Songyao Zhang,Hengqi Zou,Xinrui Miao,Wenli Deng
The self-assembly of two kinds of C2-symmetric aromatic carboxylic acids named 4,4′,4″,4‴-(1,4-phenylenebis(azanetriyl))tetrabenzoic acid (H4PTA) and 5′,5″-bis(4-carboxyphenyl)-[1,1′:3′,1″:3″,1‴-quaterphenyl]-4,4‴-dicarboxylic acid (H4QDA) and the coadsorption with coronene (COR) molecules at different solution concentrations were investigated at the heptanoic acid (HA)/highly oriented pyrolytic graphite (HOPG) interface by scanning tunneling microscopy (STM). H4PTA molecules with nonplanar conformation self-assembled into a highly ordered rhombus structure at variational concentrations and subsequently could be regulated into a Kagomé network by the coadsorption of COR molecules. H4QDA molecules with planar conformation self-assembled into two various nanostructures (rhombus structure and Kagomé network) coexisting on the HOPG surface at different concentrations. The Kagomé architecture of H4QDA could act as a rigid host template to trap the COR molecules. Meanwhile, COR exhibited preferential adsorption in the porous template: COR only entered the hexagonal cavities at low concentrations and filled in all hexagonal and triangular cavities at high concentrations. Density functional theory (DFT) calculations and molecular dynamics (MD) simulations showed that the host–guest co-assembled structures were more thermodynamically and kinetically stable. The formation of different self-assembly and co-assembly processes of two molecules could be attributed to the dissimilar molecular conformation. Our work is of significance to further explore the formation mechanism of two-dimensional (2D) porous arrangements and provides an ideal way to regulate the adsorption of porous templates.
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APPLIED SURFACE SCIENCE
·
2022
·
IF 7.392
Fangfang Chang,Juncai Wei,Yongpeng Liu,Wenwen Wang,Lin Yang,Zhengyu Bai
Converting CO 2 to value-added chemicals and fuels by the electrocatalytic reduction reaction (CO 2 RR) is a promising strategy for reducing CO 2 emissions and achieving clean energy storage. Herein, Cu 2 O catalysts with various morphologies (hexapod concave rhombic dodecahedrons microcrystals enclosed with (3 3 1), (1 1 1) and (1 0 0) facets (D-Cu 2 O), cubic microcrystals enclosed with (1 0 0) facet (C-Cu 2 O) and octahedron microcrystals with (1 1 1) and (1 0 0) facets (O-Cu 2 O)) are prepared via the wet chemical reduction method. The in-situ formation of D-Cu 2 O/Cu, C-Cu 2 O/Cu and O-Cu 2 O/Cu surface/interface and the conversion mechanism of CO 2 to C 2+ products have been systematically studied. The electrocatalytic performance of D-Cu 2 O/Cu for CO 2 to form C 2+ products is superior to that of C-Cu 2 O/Cu and O-Cu 2 O/Cu, which the Faraday efficiencies (FE) of C 2+ products (ethylene and ethanol) reaches 70 %. The experimental results combined in-situ Raman spectroscopy and density function theory (DFT) calculations demonstrate that the good electrochemical performance is relate to the surface reconstruction and facet interface, which provides a positive local electronic environment to enhance the adsorption of *CO intermediates and reduces the energy barrier for the activation the C C coupling. This study will provide a new approach to improve the selectivity of CO 2 RR by interface engineering and surface.
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APPLIED CATALYSIS B-ENVIRONMENTAL
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2026
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IF 19.7
Yingchen Xu,Pengda Hong,Tong Bian,Caili Lu,Huijun Yu,Yuming Zhou,Yiwei Zhang
A seed self-sacrificial strategy was proposed to prepare Cu 2 O/MOF composites with tunable MOF lengths. • The synthesized MOF exhibited unique CO 2 adsorption capacity , with an optimal value of 97.50 cm 3 /g. • Tuning outer MOF length modulated CO 2 adsorption, enabling selective control over C 1 and C 2 conversion. • When the outer MOF layer reached 500 nm, Cu 2 O/MOF-2 achieved optimal C 2 selectivity with an FE of 81.43% and 16 h stability. • In situ FTIR and DFT showed that MOF-enhanced CO 2 adsorption raised *CO coverage on Cu 2 O/MOF, lowering C 2 formation barrier. In the electrocatalytic process of Carbon dioxide reduction reaction (CO 2 RR), one of the challenges faced by copper (Cu)-based MOF catalysts is insufficient structural stability, which leads to low utilization of active sites and reduced product selectivity. This study proposed a seed self-sacrifice strategy to fabricate Cu 2 O/MOF composite materials with tunable metal-organic framework (MOF) lengths, where cuprous oxide (Cu 2 O) serves as a metal-source seed to support the growth of the outer MOF. By regulating the length of the outer MOF material, the degree of CO 2 concentration can be modulated, thereby enabling precise control over the conversion rates of C 1 and C 2 products. In particular, when the length of the outer MOF is approximately 500 nm, Cu 2 O/MOF-2 achieves the highest selectivity for C₂ products, reaching 81.43%. In-situ Fourier-transform infrared spectroscopy measurements and density functional theory calculations reveal that the MOF with an appropriate length exhibits optimal adsorption effects for CO 2 . This increases the coverage of the *CO adsorption layer at the Cu 2 O/MOF interface, thereby lowering the energy barrier for C 2 products formation and accelerating the generation of ethylene and ethanol. This study pioneeringly establishes a novel pathway for selectively obtaining high-value energy products by controlling the component length. Download: Download high-res image (179KB) Download: Download full-size image The Cu 2 O/MOF composites with tunable MOF lengths were fabricated via a seed self-sacrifice strategy. By modulating the length of the outer MOF, the CO 2 concentration could be regulated, which promoted the formation and concentration of *CO. This process increased the coverage of the *CO adsorption layer on the Cu 2 O/MOF and lowered the energy barrier for the formation of the *CO*CO intermediate, thereby enabling the efficient generation of C 2 products.
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ENERGY & FUELS
·
2025
·
IF 5.3
Tianxiang Guo,Changxin Ma,Xilai Wang,Zijun Men,Baijiang Liu,Alemayehu Hailu Bedane
The electrochemical reduction of CO2 to high-value C2 products, particularly ethanol, represents a promising strategy for mitigating greenhouse gas emissions and addressing climate challenges. However, the rational design of efficient electrocatalysts for this process remains hindered by insufficient activity, selectivity, and mechanistic understanding. So, this work developed a hierarchically structured copper–zinc bimetallic catalyst (CuZn-DAT) via a novel potential-step electrodeposition (PSE) method, employing diaminotriazole (DAT) as both a morphology-directing agent and electronic stabilizer. Multimodally comprehensive characterization (BET/SEM/TEM/XRD/EDS/ICP-OES/XPS) revealed a three-dimensional porous architecture with optimized electronic configurations, where Zn alloying narrowed the HOMO–LUMO gap, while DAT coordination suppressed Cu surface reconstruction. Electrochemical evaluations (CV/LSV/EIS/GC/1H NMR) demonstrated exceptional CO2-to-ethanol conversion performance, achieving a total Faradaic efficiency (FE) exceeding 75% at current densities above 50 mA cm–2, with ethanol dominating C2 products at 87% selectivity (FEethanol = 19.9%). Zn incorporation boosted FEethanol and partial current density by 325 and 600%, respectively, while subsequent DAT modification further enhanced these metrics by 194 and 292%. Mechanistic studies combined with density functional theory (DFT) calculations identified the accelerated *CO dimerization kinetics and stabilized *CO–CHO intermediates as critical factors. A dominant stepwise reaction pathway of CO2-to-ethanol conversion on the CuZn-DAT catalyst was established as CO2 (g) → *CO2 → *CO2– → *COOH → *CO → *CHO → *CO–CHO → *OHCH2CH3 → CH3CH2OH (l). This work establishes a dual-modification strategy (Zn alloying + organic stabilization) that advances the development of efficient electrocatalysts for sustainable CO2-to-ethanol conversion, providing fundamental insights into C–C coupling mechanisms and catalyst design principles for multicarbon product formation.
研究领域:
材料科学
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电化学
·
理论计算
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DOI
高影响因子
ACS Applied Materials & Interfaces
·
2025
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IF 8.2
Changjiang Liu,Hu Zang,Xin Liu,Haiyan Lu,Nan Yu,Baoyou Geng
Copper-based catalysts demonstrate distinctive multicarbon product activity in the CO2 electroreduction reaction (CO2RR); however, their low selectivity presents significant challenges for practical applications. Herein, we have developed a multilevel porous spherical Cu2O structure, wherein the mesopores are enriched with catalytic active sites and effectively stabilize Cu+, while the macropores facilitate the formation of a “gas–liquid–solid” three-phase interface, thereby creating a microenvironment with an increasing water concentration gradient from the interior to the exterior. Potential-driven phase engineering and protonation synergistically optimize the reaction pathway, facilitating a switch between CO and C2H4. At a low current density of 100 mA cm–2, the faradaic efficiency (FE) for CO reaches an impressive 96.97%. When the current density increases to 1000 mA cm–2, FEC2H4 attains 53.05%. Experiments and theoretical calculations indicate that at lower potentials, the pure Cu2O phase diminishes the adsorption of *CO intermediates, while weak protonation inhibits hydrogen evolution reactions, thereby promoting CO production. Conversely, at more negative potentials, the Cu0/Cu+ interface and strong protonation generate locally elevated concentrations of *CO and *COOH intermediates, which enhance C–C coupling and deep hydrogenation, ultimately improving selectivity toward C2+ products. This study provides novel insights into the rational design of copper-based catalysts for customizable CO2 electroreduction products.
研究领域:
材料科学
·
电化学
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PubMed
高影响因子
Reaction Kinetics Mechanisms and Catalysis
·
2017
·Vol. 122
·期 2
·1031-1047
·
IF 1.264
Meng Chen,Cao Gui-Ping,Yan Yi-Zhen,Zhao En-You,Hou Lin-Yi,Shi Hua-Yi
In this work, during the synthesis and hydrolysis of cellulose acetate propionate (CAP), the research not only focused on the contents, but also the distributions of acetyl and propionyl groups in the different positions of anhydroglucose unit, i.e. C2, C3 and C6. It was investigated that cellulose propionylation was more difficult than acetylation, which required larger amounts of reagents. At the same temperature, the reaction rate constant of cellulose acetylation was much higher than that of propionylation. Furthermore, the partial degrees of propionyl substitution in CAP were 0.54, 0.54, and 0.48 for C2, C3, and C6. The contents of propionyl distributed on C2 and C3 positions were higher than that on C6 indicating that acetyl took the position of C6 preferentially. During the hydrolysis of CAP, the degrees of hydrolysis were 0.1 for acetyl and 0.3 for propionyl. Acetyl groups in the C6 position and propionyls in the C2 position were hydrolyzed much easier with the degrees of hydrolysis of 0.16 and 0.32, respectively. In addition, it has been investigated that hydroxyl groups in the C3 position exhibited the lowest reactivity during the synthesis of CAP, while acyl groups on C3 was also the hardest to be hydrolyzed.
研究领域:
材料科学
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化学工程
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高影响因子
RSC Advances
·
2021
·Vol. 11
·期 61
·38486-38494
·
IF 3.361
Jun-Hao Zhou,Chen-Yue Yuan,Ya-Li Zheng,Hai-Jing Yin,Kun Yuan,Xiao-Chen Sun,Ya-Wen Zhang
Tandem catalysis, in which a CO2-to-C2 process is divided into a CO2-to-CO/*CO step and a CO/*CO-to-C2 step, is promising for enhancing the C2 product selectivity when using Cu-based electrochemical CO2 reduction catalysts. In this work, a nanoporous hollow Au/CuO–CuO tandem catalyst was used for catalyzing the eCO2RR, which exhibited a C2 product FE of 52.8% at −1.0 V vs. RHE and a C2 product partial current density of 78.77 mA cm−2 at −1.5 V vs. RHE. In addition, the C2 product FE stably remained at over 40% over a wide potential range, from −1.0 V to −1.5 V. This superior performance was attributed to good matching in terms of the optimal working potential and charge-transfer resistance between CO/*CO-production sites (Au/CuO) and CO/*CO-reduction sites (CuO). This site pair matching effect ensured sufficient supplies of CO/*CO and electrons at CuO sites at the working potentials, thus dramatically enhancing the formation rate of C2 products.
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高影响因子
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