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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DOI
高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
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2023
·
IF 3.8
Huijun Shang,Hengli Li,Weijun Li,Feng Pan,Zhan Du
ABSTRACT In order to avoid the formation of η phase (W 6 Co 6 C or W 3 Co 3 C) that adversely affects the sintering process and its products in the preparation process of ultra-fine WC-Co powder, a technical route of pre-reduction of WO 3 –Co 3 O 4 to WO 2 –Co and then deep reduction carbonization to WC-Co powder has been proposed. This study mainly investigates the influence of gas partial pressure on the pre-reduction process of WO 3 –Co 3 O 4 under a mixed atmosphere of H 2 –C 2 H 4 –Ar at 600 °C and establishes the kinetic equations of pre-reduction and carbon evolution. The results indicate that increasing the partial pressure of hydrogen is conducive to the rapid and complete conversion of WO 3 to WO 2 . High carbon content can be generated by the deposition of C 2 H 4 , and it hinders the diffusion of the reducing gas; WO 3 still cannot be completely reduced to WO 2 as the partial pressure of C 2 H 4 increases to 60%. For the carbon evolution of C 2 H 4 , the carbon amount is positively related to the H 2 partial pressure, but it shows the highest amount and evolution rate when the ethylene partial pressure is 20%. Based on the reduction rate curves of WO 3 and carbon evolution rate curves of C 2 H 4 , the rate equations of pre-reduction and carbon evolution of WO 3 –Co 3 O 4 system at 600 °C are established. The pre-reduction reaction belongs to the first-order reaction, and its equation is expressed as follows: r = − d w WO 3 d t = 9 ± 0.15 × 1 0 − 2 P H 2 0.44 P C 2 H 4 0.57 The carbon deposition rate equation of C 2 H 4 can be expressed as follows: r ' = d c C d t = r f − r b ≅ 7.35 × 1 0 − 2 × P C 2 H 4 0.31
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Yuxiu Sun,Qianqian Yu,Chenxu Geng,Gui-Rong Zhang,Zhengqing Zhang,Zhihua Qiao,Chongli Zhong
Membrane technology based on ethane-selective permeation materials is highly imperative for energy-efficient separating C 2 H 6 and C 2 H 4 mixture. Herein, we rationally constructed a fluorinated metal–organic framework based mixed matrix membrane (MMM), which can selectively permeate ethane from a C 2 H 6 /C 2 H 4 mixture. The unique structure of MOF-808 allows functionalization of fluorinated carboxylic acid (FCA) in the MOF framework to construct various fluorinated MOFs via a facile post-synthetic strategy. As a proof of concept, four FCAs with different fluorocarbon chain lengths, including trifluoroacetic acid (TFA), pentafluoropropionic acid (PFPA), heptafluorobutyric acid (HFBA), and perfluorovaleric acid (PFVA), were used to create fluorinated MOFs and corresponding MMMs. The typical HFBA-MOF/PIM-1 hybrid membrane exhibits a high C 2 H 6 /C 2 H 4 selectivity of about 2.3 with C 2 H 6 permeability of 4246 Barrer at 253 K and 6 bar. Computational simulations confirm that the reversed permeation behavior is attributed to the strong affinity of C 2 H 6 within the fluorinated pore environment, mediated by multiple hydrogen bonds.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2022
·
IF 24.319
Honglin Li,Shoufu Cao,Hongman Sun,Yonglian Lu,Ying Zhang,Xiaoqing Lu,Jingbin Zeng,Zifeng Yan
Copper (Cu) has been proved as an efficient catalyst in carbon dioxide electrochemical reduction reaction (CO 2 RR) towards hydrocarbons, but still suffers from low selectivity and poor stability. Herein, Cu-based/CxNy catalysts were fabricated by facile pyrolysis of CuNCN in sealed quartz tubes. It is found that CuNCN pyrolyzed at 300 °C (CuNCN-300) exhibits a high C 2 H 4 Faradaic efficiency of 48.5% at 500 mA cm - 2 . However, increasing the pyrolysis temperature above 400 °C gives rise to CH 4 being the predominant product and CuNCN-500 achieves CH 4 Faradaic efficiencies of 66.3% at 300 mA cm - 2 . Combining experimental and DFT calculation results, Cu 3 N plays a crucial role in the formation of C 2 H 4 , while tri-s-triazine units in CuNCN-500 reduce the barrier of *CO hydrogenation to *CHO and retard C-C coupling on Cu surface. These findings mark the significance of precise tailoring of the synergistic effect between g-C 3 N 4 and different Cu species for achieving the desired selectivity during CO 2 RR.
研究领域:
材料科学
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电化学
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理论计算
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DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2024
·
IF 4.8
Rongqing Qin,Ziqi Zhao,Na Shi,Guanyu Chen,Mei Yang,Qinggang Ren,Hongbing Ji,Kungang Chai
The separation of propylene (C 3 H 6 ) and ethylene (C 2 H 4 ) during the methanol-to-olefin (MTO) process is crucial yet challenging. Herein, we report a covalent organic framework (TzDva) featuring favorable nitrogen adsorption sites and vinyl modification for the capture of C 2 H 4 from C 3 H 6 /C 2 H 4 mixtures. TzDva exhibits enhanced crystallinity and porosity as well as reduced pore size compared to its vinyl-free counterpart (TzPA), as revealed through comprehensive characterization. The excellent performance of TzDva for C 3 H 6 /C 2 H 4 separation combined with its excellent recyclability was confirmed by both static adsorption and dynamic breakthrough experiments. Particularly, it exhibits a C 2 H 4 productivity of 4.29 mmol g −1 at 298 K with C 3 H 6 /C 2 H 4 (10/90) mixture. With decreasing temperature to 273 K, the performance can be further enhanced. Theoretical calculations and in-situ infrared analysis suggested that the remarkable selectivity of TzDva towards C 3 H 6 stems from its favorable pore environment, which facilitates a greater number of interactions with C 3 H 6 compared to C 2 H 4 guests. These results underpinned the effective separation of gas mixtures relevant to the MTO process.
研究领域:
化学工程
·
材料科学
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高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2026
·
IF 9.1
Linxuan Han,Yutao Liu,Dongxiao Yang,Jian Tan,Chao Zhi,Yang Chen,Jinping Li,Libo Li
Membrane separation technology on account of low energy consumption shows great potential for energy-intensive C 2 H 4 /C 2 H 6 separation. Mixed matrix membranes (MMMs), fabricated by embedding sieving functional fillers within polymer, are expected to improve the separation performance of conventional polymer. However, most MMMs fail to deliver the anticipated gains in C 2 H 4 /C 2 H 6 separation selectivity. Sieving fillers typically have ultra-small pores that may impose higher entry barriers on polarizable hydrocarbons than the dynamic free-volume elements of polymers. Thus, focus should extend beyond the filler itself to the structural variations of the polymer matrix upon filler incorporation. In this work, we incorporated an C 2 H 4 /C 2 H 6 sieving metal-organic framework material, Cu(BF 4 ) 2 (4-DPDS) 2 , into 6FDA-DAM to fabricate MMMs for C 2 H 4 /C 2 H 6 separation. It is found that the size sieving ability of Cu(BF 4 ) 2 (4-DPDS) 2 contributes partially to the improved C 2 H 4 /C 2 H 6 diffusion selectivity. Additionally, the rigidification of 6FDA-DAM molecular chains induced by the strong interfacial interaction markedly hinders C 2 H 6 transport. These two factors act synergistically to effectively enhance the C 2 H 4 /C 2 H 6 diffusion selectivity. For an equimolar gas mixture, the filler-optimized MMMs exhibit a C 2 H 4 permeability of 13.35 barrer and a C 2 H 4 /C 2 H 6 selectivity of 7.02, exceeding the separation upper bound reported in 2013 and representing the highest selectivity reported for sieving-filler-based MMMs. This work provides valuable insights for the rational design of high-performance MMMs for ethylene/ethane separation.
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DOI
高影响因子
Industrial Chemistry & Materials
·
2025
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IF 11.9
Longlong Wang,Ruirui Wang,Shuang Wei,Kexin Li,Hasnain Nawaz,bin He,Mengyue Li,Ruixia Liu
Photothermal synergistic catalysis significantly enhances the efficiency of photocatalytic CO2 reduction, offering a promising strategy for accelerated CO2 resource utilization. Herein, a series of CuxInyS photocatalysts were synthesized, exhibiting tunable band gap energy by varying the Cu/In/S atomic ratios for photothermocatalytic CO2 conversion to C2H4. The typical CuInS2 demonstrates a more negative conduction band, significantly enhancing electron reduction ability and facilitating the multi-electron reduction of CO2 to C2H4. Additionally, the high sulfur vacancy in CuInS2 generates additional active sites, enhances charge separation efficiency, and consequently improves catalytic activity. The generation rate of ethylene reaches 45.7 μmol·g-1·h-1 with the selectivity of 79.7%. This study provides a new avenue for producing ethylene in photothermal catalysis, as well as highlights the superiorities of CuInS2 catalyst.
研究领域:
材料科学
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环境科学
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能源化学
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DOI
高影响因子
CARBON
·
2019
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IF 7.466
Hui Ning,Xiaoshan Wang,Wenhang Wang,Qinhu Mao,Zhongxue Yang,Qingshan Zhao,Yan Song,Mingbo Wu
Electroreduction of carbon dioxide (CO 2 ) to ethylene (C 2 H 4 ) is one of the most feasible approaches to reduce the carbon emissions and enhance carbon dioxide utilization , whereas the lack of efficient catalysts impedes the scale application. Cuprous oxide (Cu 2 O) is a promising catalyst for the formation of C 2 H 4 but with unsatisfied selectivity and stability. Herein, we prepared Cu 2 O/nitrogen-doped carbon shell (Cu 2 O/NCS) composite and employed it in the production of C 2 H 4 from CO 2 electroreduction. The ultra-thin NCS with graphene-like structure was prepared from petroleum asphalt by template method . The cubic Cu 2 O nanocrystals are uniformly dispersed on the surface of NCS with ca. 150 nm diameters. Cu 2 O/NCS loaded on glass carbon electrode showed a high faradaic efficiency of C 2 H 4 (24.7%) at −1.3 V ( vs . reversible hydrogen electrode) as well as remarkable stability. The excellent performance of Cu 2 O/NCS is attributed to the high dispersion of cubic Cu 2 O nanocrystals and the abundant pyridinic-N moieties in NCS. This work provides a new strategy to improve the selectivity and durability of Cu 2 O for production C 2 H 4 from electrocatalytic CO 2 reduction by fabricating composites with nitrogen-doped carbon materials.
研究领域:
材料科学
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环境科学
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电化学
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DOI
高影响因子
ACS Catalysis
·
2026
·Vol. 16
·期 15
·15348-15362
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IF 13.6
Rhimi Baker,Harrath Karim,Liu Yifan,Liu Zheyang,Zhou Min,El-Khodary Sherif A.,Shi Weidong,Jiang Zhifeng
Photocatalytic CO 2 reduction to C 2 H 4 remains challenging due to inefficient multielectron transfer and sluggish C−C coupling kinetics. Herein, we demonstrate that precise engineering of metal−organic framework (MOF) nodes establishes dual-functional active sites that synergistically drive C−C coupling and H 2 O activation. A hybrid photocatalyst is constructed by integrating a porphyrinic MOF (Fe-MOFBPy), featuring axially coordinated bipyridine ligands that modulate paddlewheel Fe−N nodes, with carbon nitride (CN) to form a heterojunction. Controlled linker depletion introduces defects that generate coordinatively unsaturated Fe sites and enable rational tuning of Fe−N bonding. Combined density functional theory and ab initio molecular dynamics simulations reveal that the Fe−N bond acts as a dual-functional site, where the N atom facilitates H 2 O activation and proton transfer, while the Fe center promotes *CO + *CHO coupling toward C 2 intermediates. In contrast, defective MOFs with reduced Fe−N coordination form Fe−O sites that exhibit inferior activity due to inefficient H 2 O activation. Notably, the intrinsic flexibility of the Fe−N bond lowers the kinetic barrier for H 2 O dissociation. Consequently, the catalyst achieves a C 2 H 4 production rate of 24.5 μmol g −1 h −1 with an 87.1% electron-based selectivity, outperforming analogous systems. This work provides a blueprint for designing dual-functional sites in MOFs for solar-driven C 2 H 4 synthesis.
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高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2021
·
IF 7.312
Shao-Min Wang,Fei Wang,Yong-Li Dong,Mohana Shivanna,Qiubing Dong,Xuan-Tong Mu,Jingui Duan,Qingyuan Yang,Michael J. Zaworotko,Qing-Yuan Yang
The separation of ethane (C 2 H 6 ) from ethylene (C 2 H 4 ) is one of the most challenging and important tasks in chemical industry. Herein we report two interpenetrated diamondoid ( dia ) coordination networks, Dia-4-M [M(pba) 2 ] (pba = 4-(4-pyridyl)benzoate); M = Ni or Co), that can directly capture ethane from ethane-ethylene mixtures with reverse C 2 H 6 /C 2 H 4 separation. Both materials not only exhibit ultra-high C 2 H 6 uptake (100 cm 3 g −1 for Dia-4-Ni ; 103 cm 3 g −1 for Dia-4-Co ) but also display good C 2 H 6 /C 2 H 4 selectivity (1.76 for Dia-4-Ni ; 2.04 for Dia-4-Co ). Such C 2 H 6 /C 2 H 4 separation performance was confirmed by dynamic breakthrough experiments. Dia-4-M could extract low concentrated of C 2 H 6 from C 2 H 6 /C 2 H 4 mixture (v(C 2 H 6 )/v(C 2 H 4 ) = 1:9 and 1:15) and produce high purity (99.9%) of C 2 H 4 under ambient conditions. The mechanism for selective C 2 H 6 /C 2 H 4 separation was clarified through Grand Canonical Monte Carlo (GCMC) simulations and Density functional theory (DFT) calculations. Overall, this research demonstrates that Dia-4-M has a significant potential as effective C 2 H 6 -selective adsorbents for the purification of ethylene in practice.
研究领域:
化学工程
·
材料科学
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DOI
高影响因子
Small
·
2026
·
IF 11.8
Zhenliang Zhu,Jianfei Xiao,Ruiyao Li,Yaoqi Huang,Shaojun Yuan
Ultramicroporous MOFs capable of simultaneously separating C 2 H 6 /C 2 H 4 and C 2 H 2 /CO 2 mixtures remain rare due to the stringent requirements on pore confinement and adsorption-site distribution. Here, we report a dual-ligand engineered porphyrin-based framework, Zn-TCPP-mtz, constructed from Zn 2+ nodes, tetrakis(4-carboxyphenyl)porphyrin (TCPP), and 5-methyl-1H-tetrazole (mtz). The incorporated mtz ligands bridge adjacent porphyrin layers and, together with interlayer hydrogen-bonding interactions, result in a compact stacking arrangement featuring 1D ultramicropores (7.2 × 4.8 Å 2 ) decorated with N/O functional sites and hydrophobic methyl groups. This tailored pore environment enables Zn-TCPP-mtz to adsorb 2.63 and 2.56 mmol g −1 of C 2 H 6 and C 2 H 4 , respectively, as well as 3.14 and 1.89 mmol g −1 of C 2 H 2 and CO 2 at 298 K and 1 bar, achieving selectivities of 1.5 for C 2 H 6 /C 2 H 4 and 3.1 for C 2 H 2 /CO 2 . Dynamic breakthrough experiments confirm one-step production of high-purity C 2 H 4 (>99.9%) and C 2 H 2 (>99.5%) with productivities of 3.0 and 16.3 L kg −1 , respectively. DFT calculations reveal that the ultramicroporous channels provide well-defined interaction sites that stabilize C 2 H 6 over C 2 H 4 and C 2 H 2 over CO 2 through multiple dispersion-dominated contacts. This study demonstrates that the dual-ligand strategy can be extended to construct porphyrin-based frameworks with controlled pore architectures and stable adsorption environments, enabling the integration of multiple C 2 gas separations within a single material platform.
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DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
·
2022
·
IF 8.047
Jing Huang,Jiawei Dai,Jiannan Zhu,Rong Chen,Xiaoqi Fu,Hongfang Liu,Guangfang Li
Electrocatalytic reduction of CO 2 (CO 2 RR) represents a promising approach to reduce CO 2 emission and generate value-added chemicals. Herein, we developed bimetallic Au-Cu gradient alloy nanostructures (AuCu-g) comprising of ultrathin Cu-rich alloy surface and Au-rich alloy core as electrocatalyst via a facial solvothermal method. Impressively, the AuCu-g can stably generate a considerable amount of C 2 H 4 with faradaic efficiency (FE) ∼20 % at a low limiting potential of −0.4 V versus reversible hydrogen electrode (RHE) due to its unique gradient structure and multi-component tandem effect. The potential-dependent in situ Raman spectrum indicated an enhanced *CO adsorption strength and a remarkable CO intermediate generation over Au-Cu gradient alloy at low overpotentials during CO 2 reduction process. This work shines a light for developing mutilmetallics toward efficient CO 2 RR.
研究领域:
材料科学
·
电化学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）