POLYMER
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2024
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IF 4.1
Ran Liang,Linyu Wang,Youfa Wang,Fan Zhou,Zibo Yang,Yuxiu Sun,Zhenjie Gu,Zhihua Qiao
Methane/nitrogen (CH 4 /N 2 ) separation remains a persistent challenge owing to the similar polarities, kinetic diameters, and boiling points of CH 4 and N 2 . Herein, a novel method is proposed for enhancing the separation performance of CH 4 /N 2 via vacuum resistance calcination, which uses surface-carbonized and hardened ZIF-8 (SCH-Z), MOF-74-Ni (SCH-M), and UiO-66-NH 2 (SCH–U). The nanoparticles treated by vacuum resistance calcination remain the microporous characteristics of MOF, while introducing additional mesoporous structure and unsaturated metal sites. Such multistage pore structure and rich metal sites display a significant improvement in the CH 4 adsorption over N 2 . In addition, the separation performance of multiple metal–organic frameworks (MOFs) mixed matrix membranes (MMMs) fabricated by homogeneously mixing the alkaline polymer polyvinylamine (PVAm) with SCH-M/SCH-Z and SCH-M/SCH–U was investigated, respectively. When the measured pressure was 0.1 MPa and the binary filler loading was 48 %, the PVAm/(SCH-M) 0.7 (SCH-Z) 0.3 /MPSf MMM exhibited outstanding CH 4 /N 2 separation performance (CH 4 permeance of 2888.48 GPU and selectivity of 4.38). Furthermore, when the loading of the binary filler was 45 %, the ideal CH 4 /N 2 selectivity and CH 4 permeance of PVAm/(SCH-M) 0.67 (SCH–U) 0.33 /MPSf MMM are 5.57 and 2263.94 GPU, respectively. This study provides a novel idea that introducing multi-MOF nanoparticles into MMMs for optimizing gas separation performance.
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
Journal of the American Chemical Society
·
2024
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IF 14.4
Yao Song,Xiao Yang,Huan Liu,Suxia Liang,Yafeng Cai,Wenqiang Yang,Kaixin Zhu,Liang Yu,Xiaoju Cui,Dehui Deng
Electrochemical conversion of CH4 to easily transportable and value-added liquid fuels is highly attractive for energy-efficient CH4 utilization, but it is challenging due to the low reactivity and solubility of CH4 in the electrolyte. Herein, we report a high-pressure electro-Fenton (HPEF) strategy to establish a hetero-homogeneous process for the electrocatalytic conversion of CH4 by O2 at room temperature. In combination with elevation of reactant pressure to accelerate reaction kinetics, it delivers an unprecedented HCOOH productivity of 11.5 mmol h–1 gFe–1 with 220 times enhancement compared to that under ambient pressure. Remarkably, an HCOOH Faradic efficiency of 81.4% can be achieved with an ultralow cathodic overpotential of 0.38 V. The elevated pressure not only promotes the electrocatalytic reduction of O2 to H2O2 but also increases the reaction collision probability between CH4 and •OH, which is in situ generated from the Fe2+-facilitated decomposition of H2O2.
研究领域:
环境科学
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电化学工程
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PubMed
高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
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2026
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IF 3.2
Xiaowen Li,Chenyu Chu,Jiahua Cheng,Le Chen,Zhihui Zhang,Yong Jin,Chuan Jiang,Goujian Ji
Bromine functionalization improves low-pressure CH 4 /H 2 separation in UiO-66. • UiO-66-Br 2 shows the highest CH 4 /H 2 selectivity among the three samples. • Bromination strengthens CH 4 -framework interactions and favors CH 4 adsorption. • Bromination leads to a capacity-selectivity trade-off in the UiO-66 series. Efficient separation of CH 4 /H 2 mixtures is crucial for hydrogen purification but remains challenging because of the limited adsorption contrast between the two gases in conventional porous adsorbents. Herein, UiO-66 and its brominated derivatives, UiO-66-Br and UiO-66-Br 2 , were synthesized and systematically investigated through structural characterization, adsorption measurements, ideal adsorbed solution theory (IAST), grand canonical Monte Carlo (GCMC) simulations, and density functional theory (DFT) calculations. Bromination preserved the parent UiO-66 framework while effectively regulating the pore environment and host-guest interactions. At 273 K and 1 bar, the experimental CH 4 uptake increased from 0.809 mmol g −1 for UiO-66 to 0.938 mmol g −1 for UiO-66-Br 2 . Both IAST and binary GCMC consistently demonstrated enhanced CH 4 /H 2 separation after bromination, with UiO-66-Br 2 exhibiting the best overall performance. In particular, binary GCMC simulations yielded a CH 4 /H 2 selectivity of 14.23 for UiO-66-Br 2 at 0.1 bar, representing an approximately 73 % enhancement over pristine UiO-66 (8.23). DFT calculations further revealed that the CH 4 binding energy increased from 7.097 kJ mol −1 for BDC to 26.433 kJ mol −1 for BDC-Br 2 , indicating substantially strengthened local CH 4 -linker interactions. These results demonstrate that bromine functionalization, particularly dibromination, effectively enhances CH 4 -preferential adsorption and CH 4 /H 2 separation through the synergistic regulation of pore confinement and host-guest interactions. Download: Download high-res image (401KB) Download: Download full-size image
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SEPARATION AND PURIFICATION TECHNOLOGY
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2025
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IF 9
Tong Huang,Qiuyu Wu,Dong Qi,Feifan Yang,Yaqiong Xie,Guangru Zhang,Xin Liu,Gongping Liu,Haipeng Zhu
Natural gas upgrading demands advanced CO 2 /CH 4 separation membranes for CO 2 removal. Polymer of intrinsic microporosity (PIM-1) represents a novel polymeric molecular sieve featuring exceptional permeability and processability, but its moderate CO 2 /CH 4 selectivity remains challenging. Plasma treatment, a well-applied technique for surface modification of dense polymers, has been adopted to PIM with abundant interchain micropores for the first time. The physical alteration of plasma treatment in He gas atmosphere, primarily the chain scission, has significant impacts on CO 2 /CH 4 separation performance of PIM-1 membrane, by means of regulating its hierarchical microporous structure. Wide angle X ray scattering (WAXS) results suggest that the relatively large micropores are more prone to shrinkage and collapse than relatively small ones, which effectively enhances the selectivity. Moreover, owing to near-surface localization effect, the plasma modification is constrained within a skin layer onto a bulk intact layer. This asymmetric membrane structure allows the balance of enhancing CO 2 /CH 4 selectivity and sustaining high CO 2 permeability. By optimizing plasma input power and duration, the selectivity of plasma-treated PIM-1 membrane increased by 1.65 times, with a high permeability of over 4000 Barrer. After 2-month aging, the permeability was still maintained 60 % of its initial value. This suggests plasma treatment as a promising post-modification method for PIM CO 2 /CH 4 separation membranes.
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高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
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2025
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IF 2.8
Chensheng Dong,Qingping Xin,Qiang Ma,Kongyin Zhao,Yupeng Kou,Yucheng Pan,Huajian Gao,Lizhi Zhao,Xiaoli Ding,YuZhong Zhang,Wei Huang,Lantian Dong,Xinqi Li
Versatile layered fluoride-cerium nanosheets with thickness about 1.60 nm denoted as F-Ce are fabricated by a convenient and environmentally friendly approach. Then, Pebax-1657 is used as the polymer matrix and F-Ce as inorganic fillers to produce mixed-matrix membranes (MMMs) for gas separation. Versatile functions in enhancing the membrane performances are exhibited by F-Ce with intrinsic dual channels. On one hand, the abundant mesoporous slits in F-Ce enhance gas diffusion, constructs high-speed transport pathways of CO 2 and improve CO 2 permeability; on the other hand, molecular-sieving d -spacing in F-Ce endows MMMs with prominently preferential CO 2 transport, which favors the increment of CO 2 /CH 4 selectivity. Furthermore, F-Ce tends to horizontal arrangement and endows the MMMs with preeminent polymer–nanosheet interfacial compatibility, thereby facilitating the superior performance of F-Ce in MMMs and leading to improvements in both permeability and selectivity. In addition, the F-Ce exhibits an affinity for CO 2 and constructs “CO 2 -philic, CH 4 -phobic” regions in MMMs, and the CO 2 -philic regions significantly improves CO 2 /CH 4 solubility selectivity and selectivity. The permeability and selectivity of MMMs in humidified state come to maximum values, 1508 Barrer and 37, respectively, at 8 wt% F-Ce loading, overcoming Robeson Upper Bound (2008). Besides, the mechanical stability of MMMs was investigated.
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高影响因子
JOURNAL OF MOLECULAR LIQUIDS
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2025
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IF 5.2
Lanyun Wang,Chao Yu,Yongliang Xu,Tingxiang Chu,Zhengyan Wu,Kun Zhang
Hydrate-based solidification of CH 4 storage and transportation is a potential technology which will be utilized in the separation of coal-bed gas, natural gas and biomass gas. Chemical additives and porous materials are usually used for accelerating the CH 4 hydrate formation and increasing the CH 4 capacity. Here, the silicon carbide foam ceramics (SFC) as a porous medium in combination with tetrabutylphosphonium bromide ([P 4 4 4 4 ]Br) and 1,3-dioxolane as chemical promoters were used to influence CH 4 hydrate formation and decomposition properties. The experimental results show that the presence of SFC leads to shortened induction time of CH 4 hydrate nucleation by 15 ∼ 25 % and increased gas storage capacity by 30 ∼ 40 % compared to that in pure water. Adding [P 4 4 4 4 ]Br reduces the induction time by only 3 %–10 % while increases gas capacity by nearly 30 %. In contrast, the 1,3-dioxlane demonstrates superior effectiveness in promoting CH 4 hydrate growth with induction time shortened by 40 %–60 %. Compared to pure water systems, SFC + 1,3-dioxolane may enhance the gas capacity of around 80 %. In terms of dissociation process, CH 4 hydrate formed in the SFC have lower dissociation temperature and shorter pre-dissociation time, indicating that hydrate formed in the porous space is easy to decompose. Moreover, after adding 1,3-dioxolane, the decomposition time was shortened further. However, 30PPI SFC is optimal for its higher dissociation temperature and longer pre-dissociation time.
研究领域:
化学工程
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材料科学
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高影响因子
Nature Communications
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2025
·Vol. 16
·期 1
·1-16
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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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DOI
PubMed
高影响因子
ACS Omega
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2020
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IF 2.87
Jianbo Zhao,Jun Wei,Di Cai,Hui Cao,Tianwei Tan
A poly(amino acid)-based approach for scalable synthesis of micro-/mesoporous carbon (PC) with high specific surface area and narrow distribution of micro- and mesopores is presented. Using cross-linked poly aspartic acid as a precursor, PC was obtained by in situ one-step carbonization without the activating agent. The resulting PC had an ultrahigh adsorption capacity for H2 (4.43 wt %) and CH4 (4.49 mmol g–1). This novel method could significantly decrease the wastewater hazards caused by washout of the considerable amount of the activating agent. The PC showed promising application in gas adsorption and storage.
研究领域:
材料科学
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能源存储
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环境科学
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DOI
PubMed
高影响因子
FUEL
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2019
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IF 5.128
Yanlei Shang,Jinchun Shi,Hongbo Ning,Runtong Zhang,Hongyan Wang,Shengnian Luo
Ignition delay times for methane/nitromethane binary fuels with oxygen diluted in Ar ( CH 4 / CH 3 NO 2 / O 2 /Ar mixtures) are measured with a heated shock tube behind the reflected shock wave at 995–1962 K and 4–18 atm for different equivalence ratios (0.5, 1.0, and 2.0). Blending ratios for CH 3 NO 2 are varied (0, 0.1, 0.2, 0.5, and 1) to investigate the promotion of CH 3 NO 2 on CH 4 during the ignition process. OH ∗ emission histories at a sidewall are used to determine the measured ignition delay times of the binary fuels mixture. Correlations for the measured ignition delay times are obtained using multiple linear regression as a function of pressure, temperature, blending ratio, and equivalence ratio. Experimental results show that a small addition of CH 3 NO 2 dramatically reduces the ignition delay times of CH 4 , and induces a weak two-stage ignition. Three literature mechanisms are examined and compared with the measured ignition delay times for CH 4 / CH 3 NO 2 binary fuels mixtures, and the mechanism from Mathieu et al. is updated and validated against the experimental data. In this mechanism, the rate constants for some important reactions are theoretically determined by quantum chemical calculation. In addition, sensitivity analysis and reaction pathway analysis as well as rate of production are carried out to further elucidate the promotion of CH 3 NO 2 on ignition of the CH 4 .
研究领域:
化学动力学
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燃烧科学
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物理化学
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2020
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IF 7.632
Zheyuan Guo,Zihan Qu,Hong Wu,Rui Zhao,Yingzhen Wu,Yutao Liu,Leixin Yang,Yanxiong Ren,Chumei Ye,Zhongyi Jiang
Well-connected transport pathways play a critical role in high-performance CO2-facilitated separation membranes. Inspired by the ionic cluster network in polymer electrolyte membranes (PEMs) for fast ion transport, designing a unique CO2-philic cluster network structure is a promising strategy to construct efficient CO2 transport channels in membranes. Herein, a forced induction method is presented to construct a CO2-philic cluster network in membranes. Sulfobutylether-beta-cyclodextrin (sβ-CD) is introduced in a quaternary ammonium polysulfone (QAPSf) matrix. During the membrane formation process, the quaternary ammonium groups on QAPSf are attracted by the sulfonic acid groups on sβ-CD, assembling around and thus forming hybrid clusters. These clusters are swollen and interconnected by water under a humidified state. The hybrid cluster network acts as an effective CO2 transport pathway via clustering quaternary ammonium ion pairs as continuous CO2-facilitated transport sites. Simultaneously, the internal cavity of sβ-CD in hybrid clusters affords additional free volume in membranes, thus enhancing the CO2 permeability. The resultant QAPSf/sβ-CD membrane exhibits an optimal CO2 permeability of 1303 Barrer, a CO2/CH4 selectivity of 39, and good long-term operation stability for 30 days, surpassing the 2008 Robeson upper bound limit. This concept of constructing a hybrid cluster network for facilitated transport is expected to be applicable to explore more advanced PEMs for effective gas separation.
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
Journal of Environmental Chemical Engineering
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2022
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IF 7.968
Tangtong Ju,Yue Dai,Hailong Tang,Meiling Wang,Xiao Sun,Min Wang,Yongqing Ma,Ganhong Zheng
Direct conversion of CH 4 to high valued chemicals under mild conditions is attractive but full of challenges. Here, we present a ternary composite that consists of Ni-doped TiO 2 nanocubes (NCs) and CNTs as a new kind of catalyst (denoted as CNTs-Ni@TiO 2 NCs) for CH 4 photocatalytic conversion to C1 oxygenated products at 30 °C. Using H 2 O 2 as an oxidant, a high C1 oxygenated products yield and selectivity of 1.43 mol/(mol Ni ·h) and 95.6% can be reached in 2 h at 30 °C. The superior photocatalytic performance resulted from the synergistic effects of TiO 2 NCs, Ni species, and CNTs such as enhanced visible light absorption , improved electron/hole separation and charge transfer property, and lowered C-H bond cleavage energy required for CH 4 activation, were carefully studied. Good reusability of the catalyst was studied by recycle experiments. Possible reaction mechanism based on the radical routes were carefully discussed by combining in-situ Fourier transform infrared spectroscopy , X-ray photoelectron spectroscopy, electron spin resonance spectroscopy, radical scavenger experiments and density functional theory calculation.
研究领域:
材料科学
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催化
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环境化学
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物理化学
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纳米技术
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DOI
高影响因子
Molecular Catalysis
·
2023
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IF 4.6
Zhishuai Wang,Fengyun Su,Hailong Cao,Mengzhen Tian,Xiang Li,Haiquan Xie,Xiaoli Jin,Zhengdao Li,Xin Ying Kong
Amidst the impending energy crisis and escalating concerns about global warming, photocatalytic reduction of carbon dioxide (CO 2 ) emerges as a promising solution. However, the practical application of this technology has been hindered by challenges such as the poor photoresponse of existing photocatalysts toward visible light, inefficient separation efficiency of photoinduced electron-hole pairs, and subpar product selectivity. This work simultaneously addresses these limitations by enhancing the activity of photocatalytic CO 2 reduction through the strategic incorporation of nickel oxide (NiO) onto niobium pentoxide (Nb 2 O 5 ). In this study, Nb 2 O 5 was prepared using the hydrothermal and calcination methods, culminating in the synthesis of NiO-supported Nb 2 O 5 achieved through the photodeposition method. The resulting 2 %-NIONBO photocatalyst with the optimal loading of NiO exhibited a remarkable methane (CH 4 ) production yield of 29.65 μmol/g/h, a striking 6.2-fold improvement over solitary NBO. In addition, the useful carbon monoxide (CO) fuel was also detected from the photoreduction of CO 2 , where 2 %-NIONBO exhibited a CO yield of 7.22 μmol/g/h, demonstrating a 3.4-fold enhancement over NBO, along with an outstanding CH 4 selectivity of 80.42 %. This study provides insights into the design and development of Nb-based photocatalysts for significantly enhanced efficiency in photocatalytic CO 2 reduction, paving the way for advancements in sustainable energy solutions and addressing environmental issues.
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高影响因子
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