JOURNAL OF MOLECULAR STRUCTURE
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2026
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IF 4.9
Di-Ming Chen,Yu-Ting Shi,Xue-Jing Zhang,Shao-Ming Fang
A robust Al-MOF built from octanuclear [Al 8 (μ 2 -OH) 8 (COO) 12 ] clusters with oxygen-rich 1D channels has been prepared. • It exhibits a high C₂H₆ uptake of 147.6 cm 3 /g and an IAST selectivity of 1.69 for equimolar C 2 H 6 /C 2 H 4 at 298 K and 1 bar. • The separation potential (ΔQ = 1.42 mmol/g) outperforms many reported Al-MOFs, reflecting a balanced capacity–selectivity trade-off. • Combined GCMC, DFT, and MD simulations reveal that multiple C–H···O contacts and greater charge transfer govern the ethane preference. The separation of ethane (C 2 H 6 ) from ethylene (C 2 H 4 ) represents a critically important yet highly challenging process in the petrochemical industry, as these two hydrocarbons possess nearly identical molecular sizes and boiling points. In this work, we report the C 2 H 6 adsorption and separation performance of a three-dimensional aluminum-based metal–organic framework (Al-MOF) constructed from octanuclear aluminum clusters and a tricarboxylate linker, featuring one-dimensional channels decorated with abundant strongly electronegative oxygen atoms originating from coordinated formate groups and μ 3 -OH moieties. The presence of these electron-rich oxygen sites creates a polar pore environment that establishes multiple C–H···O short interactions with C 2 H 6 molecules, thereby imparting a distinct recognition preference toward the paraffin over the olefin. Upon activation, the material exhibits a C 2 H 6 adsorption capacity of 147.6 cm 3 /g at 298 K and 1 bar. The ideal adsorbed solution theory (IAST) selectivity for an C 2 H 6 /C 2 H 4 (10/90) mixture reaches 1.69 at 298 K and 1 bar. Furthermore, the separation potential (Δ Q ), which integrates both adsorption capacity and selectivity, is determined to be 1.42 mmol/g, indicating a well-balanced performance profile. The different adsorption performance of 1a toward C 2 H 6 /C 2 H 4 was thoroughly studied via a combination of GCMC, DFT and MD calculations, which demonstrates that deliberate introduction of electron-rich oxygen functionalities into the pore walls of Al-MOFs represents an effective strategy for enhancing ethane-selective adsorption, positioning the present material as a competitive candidate for energy-efficient ethylene purification. Graphical -Synopsis A robust Al-MOF with octanuclear clusters and oxygen-rich pore walls was synthesized for C 2 H 6 /C 2 H 4 separation. It exhibits preferential C₂H₆ adsorption (147.6 cm 3 /g at 298 K, 1 bar), an IAST selectivity of 1.69 for equimolar mixtures, and a separation potential of 1.42 mmol/g. Combined GCMC, DFT, and MD simulations reveal that stronger C–H···O hydrogen bonding and greater charge difference lead to a more favorable host–guest interaction energy (–1.34 vs. –1.27 eV) for ethane. This work demonstrates that engineering electronegative oxygen sites in Al-MOFs is an effective strategy for energy-efficient ethylene purification. Graphical -Pictogram Download: Download high-res image (322KB) Download: Download full-size image
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Nano-Micro Letters
·
2024
·Vol. 17
·期 1
·1-17
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IF 31.6
Zhang Chaoran,Gu Yichuan,Jiang Qu,Sheng Ziyang,Feng Ruohan,Wang Sihong,Zhang Haoyue,Xu Qianqing,Yuan Zijian,Song Fang
Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO 2 reduction reaction (CO 2 RR), whereas the behavior is by far superficially understood. Here, we report that CO 2 accessibility results in a universal self-adaptive structural reconstruction from Cu 2 O to Cu@Cu x O composites, ending with feeding gas-dependent microstructures and catalytic performances. The CO 2 -rich atmosphere favors reconstruction for CO 2 RR, whereas the CO 2 -deficient one prefers that for hydrogen evolution reaction. With the assistance of spectroscopic analysis and theoretical calculations, we uncover a CO 2 -induced passivation behavior by identifying a reduction-resistant but catalytic active Cu(I)-rich amorphous layer stabilized by *CO intermediates. Additionally, we find extra CO production is indispensable for the robust production of C 2 H 4 . An inverse correlation between durability and FE CO /FE C2H4 is disclosed, suggesting that the self-stabilization process involving the absorption of *CO intermediates on Cu(I) sites is essential for durable electrolysis. Guided by this insight, we design hollow Cu 2 O nanospheres for durable and selective CO 2 RR electrolysis in producing C 2 H 4 . Our work recognizes the previously overlooked passivation reconstruction and self-stabilizing behavior and highlights the critical role of the local atmosphere in modulating reconstruction and catalytic processes.
研究领域:
材料科学
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电化学
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催化反应
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PubMed
高影响因子
ACS Applied Polymer Materials
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2025
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IF 4.7
Yucheng Wang,Fangzhe Lu,Juanqin Xue
Flexible covalent organic frameworks (COFs) are attractive due to their unique kinetic properties. However, their accessibility remains limited. In particular, it is challenging to control the flexibility of COFs, and the effects of different flexibilities on the properties of COFs are rarely revealed. In this work, three hydrazone-linked COFs with increasing flexibility were designed and synthesized by adjusting the flexibility of the hydrazide linker step-by-step. Through static adsorption and dynamic separation experiments, remarkable differences in adaptation among three COFs are revealed. The gas adsorption experiment shows that Ta-DMTH-COF has the best purification ability of C2H2/C2H4, and the selectivity of ideal adsorbed solution theory can reach 5.17, which is much higher than the other two COFs. This paper studied a flexible strategy of COFs by adjusting their connectors, and the influence of different flexibilities on the performance of COFs is analyzed, which provides an idea for the research and development of this kind of dynamic porous material.
研究领域:
材料科学
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分离技术
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共价有机框架
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气体净化
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高影响因子
ACS Applied Materials & Interfaces
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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
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电化学
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Nature Communications
·
2022
·Vol. 13
·期 1
·1-9
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IF 17.694
Liu Yuan,Liu Junhui,Xiong Hanting,Chen Jingwen,Chen Shixia,Zeng Zheling,Deng Shuguang,Wang Jun
Efficient adsorptive separation of acetylene (C 2 H 2 ) from carbon dioxide (CO 2 ) or ethylene (C 2 H 4 ) is industrially important but challenging due to the identical dynamic diameter or the trace amount. Here we show an electrostatic potential compatible strategy in a nitroprusside-based Hofmann-type metal-organic framework, Cu(bpy)NP (NP = nitroprusside, bpy = 4,4’-bipyridine), for efficient C 2 H 2 separation. The intruding cyanide and nitrosyl groups in undulating one-dimensional channels induce negative electrostatic potentials for preferential C 2 H 2 recognition instead of open metal sites in traditional Hofmann-type MOFs. As a result, Cu(bpy)NP exhibits a 50/50 C 2 H 2 /CO 2 selectivity of 47.2, outperforming most rigid MOFs. The dynamic breakthrough experiment demonstrates a 99.9% purity C 2 H 4 productivity of 20.57 mmol g −1 from C 2 H 2 /C 2 H 4 (1/99, v / v ) gas-mixture. Meanwhile, C 2 H 2 can also be captured and recognized from ternary C 2 H 2 /CO 2 /C 2 H 4 (25/25/50, v/v/v ) gas-mixture. Furthermore, computational studies and in-situ infrared spectroscopy reveal that the selective C 2 H 2 binding arises from the compatible pore electro-environment generated by the electron-rich N and O atoms from nitroprusside anions.
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
APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
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IF 21.1
Guangming Wang,Junnan Chen,Ye Qu,Yingjun Dong,Keting Wang,Lihua Qian,Rong Fu,Ying Zhang,Hui-Ming Cheng,Xiaolong Zhang
Electrochemical CO 2 reduction (ECR) to produce chemicals and fuel is a promising technique to build a net-zero carbon circular economy. The performance of ECR has largely advanced in the past decade along with the application of gas diffusion electrodes (GDEs). However, the gas-liquid balance in GDEs is highly fragile due to inefficient CO 2 mass transfer in catalyst layers, which is prone to cause the decay of catalytic performance. In this study, integrated Cu electrodes with controllable mesopores are designed and prepared by copolymer mediated electroless deposition. The optimized Cu electrode shows a selectivity of 81 % (including 65 % for C 2 H 4 ) towards C 2+ products, with a maximum C 2+ partial current density of 232 mA∙cm −2 . Further characterization and simulations reveal that the interconnected mesoporous channels stacked by in-situ reduced Cu nanoparticles leads to an improved CO 2 supply near catalytic sites. In addition, a micro-environment boosting the retention, protonation of *CO intermediates and a unique *CO-CHO coupling step is formed. Our findings provide valuable guidance for enhancing mass transfer and C-C coupling in ECR by creating and controlling intrinsic mesoporous structures in catalyst layers.
研究领域:
电化学
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材料科学
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二氧化碳利用
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纳米材料
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可持续能源
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高影响因子
Journal of Energy Chemistry
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2022
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IF 13.599
Huan Xie,Ruikuan Xie,Zhiyuan Zhang,Yongyu Pang,Yuting Luo,Jiong Li,Bilu Liu,Maria-Magdalena Titirici,Guoliang Chai
The conversion of CO 2 into value-added chemicals coupled with the storage of intermittent renewable electricity is attractive. CuO nanosheets with an average size and thickness of ∼ 30 and ∼ 20 nm have been developed, which are in situ reduced into Cu nanosheets during electrochemical CO 2 reduction reaction (ECO 2 RR). The derived Cu nanosheets demonstrate much higher selectivity for C 2 H 4 production than commercial CuO derived Cu powder, with an optimum Faradaic efficiency of 56.2% and a partial current density of C 2 H 4 as large as 171.0 mA cm −2 in a gas diffusion flow cell. The operando attenuated total reflectance-Fourier transform infrared spectra measurements and density functional theory simulations illustrate that the high activity and selectivity of Cu nanosheets originate from the edge sites on Cu nanosheets with a coordinate number around 5 (4–6), which facilitates the formation of *CHO rather than *COH intermediate, meanwhile boosting the C C coupling reaction of *CO and *CHO intermediates, which are the critical steps for C 2 H 4 formation.
研究领域:
材料科学
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电化学
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催化反应
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2026
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IF 8.8
Jianfa Liu,Yang Liu,Haonan Luo,Hui-Fang Wang,Zhenggong Wang,Jian Jin,Zheng Niu,J. Liu,Y. Liu,H. Luo,H. Wang,Z. Wang,J. Jin,Z. Niu
Hybrid membranes combine the excellent processability of polymer with the superior permeability and selectivity of porous fillers, demonstrating exceptional separation performance. However, interfacial incompatibility remains a fundamental challenge in such systems. Herein, we report a strategy incluced by molecular adsorption sites to mitigate interfacial incompatibility issues. MOF has been proved as a efficient ethyne adsorbents and applied in the separation of C 2 H 2 /C 2 H 4 . Its inorganic adsorption units, which exhibit a high affinity for ethyne, were uniformly high-quality dispersed within a polymer matrix to enable efficient C 2 H 2 /C 2 H 4 separation. The optimized hybrid membrane exhibits a 249% enhancement in C 2 H 2 /C 2 H 4 perm-selectivity compared to the pristine polymer membrane, while maintaining competitive C 2 H 2 permeability. This performance surpasses that of most reported hybrid membranes incorporating conventional fillers. Remarkably, the membranes maintain stable operation under varying pressures and prolonged testing durations. This study presents a facile yet effective strategy for fabricating high-performance gas separation membranes through the dispersion of molecular adsorption sites, opening new avenues for advanced alkyne/olefin separation.
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2020
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IF 7.183
Guining Chen,Xi Chen,Yang Pan,Yufan Ji,Gongping Liu,Wanqin Jin
Mixed-matrix membranes (MMMs) based on metal-organic frameworks (MOFs) molecular sieves have been extensively studied in gas separation due to the high performance and good compatibility of MOF with polymers. In this work, 6FDA-based polyimides MMMs incorporating M-gallate (M = Ni, Co, Mg) MOF particles were fabricated for the first time and investigated for ethylene/ethane (C 2 H 4 /C 2 H 6 ) separation. By reducing synthesis temperature and introducing agitation, the Ni-gallate particles synthesized in flask (Ni-gallate(F)) with optimized conditions are smaller than Ni-gallate synthesized in autoclave (Ni-gallate(A)). The particle size was reduced from ~7 μm (Ni-gallate(A)) to ~0.8 μm (Ni-gallate(F)), which enables the formation of uniform MMMs. Because of the better compatibility with polyimide and higher adsorption performance of Ni-gallate than Mg-gallate and Co-gallate, the 6FDA-DAM MMM containing Ni-gallate(F) was capable of simultaneously improving C 2 H 4 /C 2 H 6 selectivity and C 2 H 4 permeability whereas the MMM with Mg-gallate(F) or Co-gallate(F) failed in performance enhancement. The 6FDA-DAM MMM with Ni-gallate(F) loading of 20% exhibited optimal C 2 H 4 /C 2 H 6 separation performance that surpassed the upper-bound of pure polymers. Detailed analysis of sorption and diffusion coefficients suggested that the enhanced transport properties in Ni-gallate(F) MMMs were attributed to the increase of sorption coefficient provided by the higher C 2 H 4 sorption capacity and selectivity, as well as the favorable gas diffusivity via moderately confined pores of the incorporated Ni-gallate(F) fillers.
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
Nature Communications
·
2025
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IF 15.7
Ren Yuqi,Cheng Miao,He Hongbin,You Changjun,Duan Lunbo,Sun Zhenkun,Peng Ruoxuan,Zhu Yuan-Hao,Zhang Hongyang,Zhou Jiancheng,Huang Kai,Guan Jie,Li Naixu
CO 2 -to-hydrocarbon fuel conversion via artificial photosynthesis is limited by catalyst poisoning under high O 2 partial pressures and sluggish C 2 -product formation. Herein, Ru 0.6 Cu 1 (Cu 0 –Cu 1+ )/CeO 2 catalysts with adaptive O 2 tolerance are prepared by O 2 -mediated dynamic interfacial reconstruction. Single-atom Ru doping at Ce lattice sites creates a trigonal prismatic coordination configuration, enabling proton-coupled electron transfer and accelerating H 2 O dissociation. Photothermal effect promotes O 2 -driven self-assembly of Cu 0 –Cu 1+ charge-gradient interfaces within Ru/Cu alloy clusters, thereby optimizing the adsorption behavior of * CHOCO intermediates and restructuring the C–C coupling pathway. Interfacial charge cascade transfer and geometric site synergy thermodynamically shift the product selectivity from C 1 to C 2 , as determined by operando spectroscopy and electronic structure analysis. Under concentrated solar irradiation, the catalyst produces 549 ± 20 μmol·g −1 C 2 H 4 with 74.3% selectivity and 0.5% solar-to-chemical energy conversion efficiency—25-fold higher than that in non-concentrated systems. Dynamic interfacial regulation facilitates precise carbon chain synthesis in complex reaction networks.
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高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-16
·
IF 15.7
Zhang Zekun,Guo Hua,Li Shiji,Gao Suihan,Wang Xinyu,Li Mingtao,Yan Wei,Xu Hao
The regulation of product selectivity in electrochemical CO 2 reduction (ECO 2 R) remains fundamentally constrained by the dynamic equilibrium between intermediate transport and surface coverage. In this study, we report a progress in catalytic architecture through precision-engineered Au@Cu 2 O yolk-shell tandem nanoreactors featuring dual-tunable parameters: cavity confinement dimensions and shell thickness gradients. This structural modulation enables dynamic control over both *CO intermediate enrichment and reaction pathway bifurcation. ECO 2 R performance evaluations demonstrate significant product selectivity switching at −1.31 V (vs. reversible hydrogen electrode (RHE)). The Faradaic efficiency (FE) for CH 4 exhibits significant architectural dependence, increasing from 43.02% (thick-shell/large-cavity) to 65.54% (medium-dimension) and then decreasing to 23.26% (thin-shell/small-cavity). Conversely, the FE for C 2 H 4 demonstrates an inverse structural correlation, improving from 6.68% (medium-dimension) to 38.73% (thin-shell/small-cavity). The spatial domain-limiting mechanism of the yolk-shell structure directly controls the transition between protonation-dominated CH 4 formation and coupling-driven C 2 H 4 production. This work establishes a pioneering paradigm for dynamically steering catalytic selectivity through purely geometrical modulation, bypassing traditional compositional tuning limitations, thereby opening avenues for precision design of advanced electrocatalytic systems.
研究领域:
纳米技术
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电催化
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材料科学
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化学工程
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纳米化学
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高影响因子
PROCEEDINGS OF THE COMBUSTION INSTITUTE
·
2025
·
IF 5.2
Zhaohan Chu,Zhongkai Liu,Changyang Wang,Long Zhao,Bin Yang
An experimental study was conducted to investigate the weight growth routes from o -methylphenyl radical ( o -CH 3 C 6 H 4 ) to indene. o -Nitrosotoluene served as the precursor for o -methylphenyl radicals in this study. Co-pyrolysis of o -methylphenyl radical/C 2 H 2 and o -methylphenyl radical/C 2 H 4 was investigated utilizing the chemical microreactor and synchrotron vacuum ultraviolet photoionization mass spectrometry. Sampled mass-specific photoionization efficiency (PIE) curves were employed to identify the aromatic species, elucidating interactions between o -methylphenyl radicals and C 2 species. The species detected at m/z = 116 and 118, essential for understanding the reaction mechanism, were identified via matching photoionization cross-sections and adiabatic ionization energies with literature and theoretical values. Specifically, indene and its isomer o -methylphenylacetylene ( m/z = 116) were determined in the reaction of o -methylphenyl radical with C 2 H 2 , while indene and o -methylstyrene ( m/z = 118) were identified in the reaction of o -methylphenyl radical with C 2 H 4 . By combining the identified intermediate species with previous literature basis, the formation pathways for indene, originating from o -methylphenyl radical were discussed in both reaction systems, providing further insights for understanding the indene formation pathways.
研究领域:
物理化学
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燃烧化学
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分子反应动力学
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质谱分析
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有机反应机理
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高影响因子
危险品化学品经营许可证（带存储）