GREEN CHEMISTRY
·
2026
·
IF 10.6
Minzhi Ma,Mengge Jia,Shichu Zhao,Zhiqiang Jiang,Kangle Lv,Tongqing Li,Helei Chai,Yan Lei,Jingjing Si,Zhi Zheng,Wenjun Fa
The global imperative for carbon-neutral fuels starkly contrasts with the persistent failure to achieve solar-driven CH4/C2H6 synthesis from CO2/H2O with both high selectivity and yield, as the thermodynamic propensity for CH4/C2H6 formation collides with kinetic bottlenecks inherent in the multi-electron/proton-transfer cascade. The prevailing paradigm has long posited that CH4/C2H6 selectivity is predominantly governed by reaction kinetics rather than thermodynamics, consequently steering catalyst design toward precise modulation of reactant interfacial dynamics at catalytic surfaces. Contrary to previous assumptions, our study demonstrates for the first time that CO2 photoreduction exhibits a characteristic domino-like chain reaction mechanism: when the catalyst amounts in the reaction system reach the threshold, the reaction cascade preferentially proceeds toward thermodynamically favorable CH4 formation through low-barrier pathways, with even C2H6 generation emerging. The universality of this mechanistic paradigm has been rigorously validated across archetypal catalysts (TiO2, MoO3, CeO2, Ni/CeO2, etc.), revealing that low amounts (5.0 mg) selectively yield H2 and CO (＞60 %, 2e- transfer), whereas higher amounts (200.0 mg) drive product distribution toward thermodynamically favorable CH4 (＞50 %, 8e- transfer). To probe this mechanism, the widely utilized Ni/CeO2 was selected as the benchmark photocatalyst, where the primary constituent of the reduction product shifts from CO/H2 (＞80 %) to CH4/C2H6 (＞80 %) upon increasing Ni/CeO2 amounts. Employing quasi in situ XPS and D2O kinetic isotope effects experiments, we unveil that Ni/CeO2 suprathreshold amounts (>150 mg) create electron-enriched microenvironments at interfacial Niδ+ sites, which drive domino photoreduction of CO2 to CH4/C2H6, while kinetically quenching competing CO/H2 evolution via proton-transfer/CO-desorption impedance. Consequently, this study elucidates that the prerequisite for designing catalysts to resolve the persistent activity-selectivity trade-off is to ensure that the photogenerated carrier concentration at the active site reaches the minimum threshold required for CH4/C2+ generation.
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高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-13
·
IF 15.7
Zhang Xiuming,Jiang Yuheng,Gu Hongfei,Zhang Haoqing,Li Yuemei,Lu Zexuan,Zhang Shuping,Liu Jia,Zhang Jiatao,Tang Zhiyong
The direct oxidation of methane into methanol exploiting O 2 as oxidant offers an ideal route for methane utilization. Although the reaction is strongly preferred in thermodynamics, conventional catalytic systems always demand intense energy input like high temperatures or high-energy photons (>2.8 eV) to conquer the large kinetic barrier in the conversion process. In this study, we demonstrate that by creation of a suitable plasmonic photocatalyst, namely oxygen-vacancy-rich CuSeO 3-x , the low-energy near-infrared (NIR) photons can serve as the sole energy input to complete CH 4 -to-CH 3 OH conversion with remarkable activity (Apparent quantum yield of 1.5% at 800 nm with Au cocatalyst) and near unity selectivity (ca. 96%) at 25 °C. Such fascinating performance is attributed to a small activation energy measured at 0.28 eV, enabled by the existence of Cu II -O v species in CuSeO 3-x . Our study suggests that the ensemble of Cu II -O v constitutes an exceptional active site, which can harness the plasmon-induced hot electrons and meantime brings a kinetically advantageous route for reducing O 2 into •OH radicals greatly favoring methane activation.
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DOI
PubMed
高影响因子
Polymers
·
2024
·Vol. 16
·期 3
·393
·
IF 4.7
Xiaoyu Du,Shijun Zhao,Yanqing Qu,Hongge Jia,Shuangping Xu,Mingyu Zhang,Guoliang Geng
Imidazole ionic liquids (ILs) have good affinity and good solubility for carbon dioxide (CO2). Such ionic liquids, combined with polyimide membrane materials, can solve the problem that, today, CO2is difficult to separate and recover. In this study, the ionic liquid (IL) of 1-ethyl-3-methylimidazolium tetrafluoroborate (IL1), 1-pentyl-3-methylimidazolium tetrafluoroborate (IL2), 1-octyl-3-methylimidazolium tetrafluoroborate (IL3), and 1-dodecylimidazolium tetrafluoroborate (IL4) with different contents were added to a polyimide matrix, and a series of polyimide membranes blended with ionic liquid were prepared using a high-speed mixer. The mechanical properties and gas separation permeability of the membranes were investigated. Among them, the selectivity of the PI/IL3membrane for CO2/CH4was 180.55, which was 2.5 times higher than the PI membrane, and its CO2permeability was 16.25 Barrer, which exceeded the Robeson curve in 2008; the separation performance of the membrane was the best in this work.
研究领域:
材料科学
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环境工程
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DOI
PubMed
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Juanjuan Dai,Danyan Xie,Ying Liu,Zhiguo Zhang,Yiwen Yang,Qiwei Yang,Qilong Ren,Zongbi Bao
Supramolecular metal–organic frameworks (SMOFs) are emerging as a new family of porous materials. In this work, a SMOF, [Cu2(ade)4(H2O)2](SiF6)2 (SMOF-SIFSIX-1, ade = adenine) was successfully synthesized from the cationic complex of copper and adenine and hexafluorosilicate anions by a slow diffusion method and was demonstrated for trapping carbon dioxide in preference to methane and nitrogen. With one-dimensional pores of about 3.6 × 3.6 Å to induce their distinguishing interactions with the three components, SMOF-SIFSIX-1 exhibited excellent selective gas sorption behaviors for CO2/CH4 (50:50) and CO2/N2 (15:85) gas mixtures with ideal adsorbed solution theory selectivities of 21.1 and 131.7 at 273 K and 100 kPa pressure, respectively, outperforming most of reported hydrogen-bonded organic frameworks so far. Neutron powder diffraction and DFT-D calculations were also carried out to investigate the CO2 adsorption configuration on SMOF-SIFSIX-1a, which suggested that this framework catch CO2 due to “C···F” and “O···H” supramolecular interactions between CO2 molecules and SMOF-SIFSIX-1a. This study demonstrates that the rarely studied SMOF material shows promising potential in gas adsorption separation.
研究领域:
材料科学
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环境科学
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高影响因子
APPLIED CLAY SCIENCE
·
2020
·
IF 4.605
Xidong Du,Wenfeng Guang,Yugang Cheng,Zhenkun Hou,Zhenjian Liu,Hong Yin,Liang Huo,Ruide Lei,Couxian Shu
The greater adsorption ability of shale to CO 2 offers an alternative method to enhance shale gas recovery, where a potential solution for CO 2 sequestration into a deep shale reservoir can also be realized. Clay minerals are the important storage space for shale gas . In this work, the isotherm adsorption curves of CH 4 and CO 2 on montmorillonite at 288 K, 308 K and 328 K were obtained using gravimetric apparatus. The selectivity factor of CO 2 over CH 4 ( S CO2/CH4 ) and Henry's constants ( K H ) of CH 4 and CO 2 were calculated. More importantly, the thermodynamics parameters of CH 4 and CO 2 , including Gibbs free energy change (Δ G ), surface potential ( Ω ), isosteric heat of adsorption ( Q st ) and entropy change (Δ S ), were thoroughly analysed. The results indicate that all S CO2/CH4 values are obviously greater than one, and injecting CO 2 into a clay-rich shale reservoir to enhance the shale gas recovery is feasible. CH 4 has smaller K H than CO 2 , which shows that CH 4 has a weaker affinity on the montmorillonite surface. Low temperature helps to enlarge K H and promote the adsorption of CH 4 and CO 2 . Increasing the pressure causes the increase in Δ G and Ω of CH 4 and CO 2 . The higher Δ G and Ω of CO 2 compared to CH 4 reveal that the CO 2 adsorption on montmorillonite is more favourable and spontaneous. When the loading increases, the Q st values of CH 4 and CO 2 reduce. CH 4 has a smaller Q st than CO 2 , which suggests the stronger interaction of CO 2 with montmorillonite. CH 4 and CO 2 have decreasing Δ S with the loading. Under larger surface coverage conditions, the disorder of the adsorbed molecules is larger, and most of the injected molecules are trapped as a free state in the pore space . The higher ΔS of CO 2 illustrates that CO 2 molecules constitute a much more stable rearrangement than CH 4 molecules. The temperature has a slight effect on the Δ S of CH 4 and CO 2 .
研究领域:
地质学
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环境科学
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高影响因子
JOURNAL OF THE CHINESE CHEMICAL SOCIETY
·
2021
·Vol. 68
·期 10
·1897-1907
·
IF 1.967
Zhen Zhu,Yu-Teng Hwang,Hao-Chun Liang,Ren-Jang Wu
In this study, several Pd/MgO/BiVO 4 nanocomposites were prepared using the hydrothermal method and their effective photocatalyst activity for the photoreduction of CO 2 to CH 4 was investigated. The microstructure and photocatalytic behavior of the prepared photocatalysts were studied through X-ray diffraction, scanning electron microscopy, tunneling electron microscopy, X-ray photoelectron spectroscopy, ultraviolet–visible spectrophotometry, Fourier-transform infrared spectroscopy, Brunauer–Emmett–Teller specific surface area, and photoluminescence spectroscopy. CH 4 yields of 5.9 and 9.4 μmol g −1 hr −1 were obtained using BiVO 4 and 25% MgO/BiVO 4 nanocomposites, respectively. The highest production rate of CH 4 was measured as 12.8 μmol g −1 hr −1 on overloading 0.3% Pd on 25% MgO/BiVO 4 . Pd/MgO/BiVO 4 exhibited excellent CO 2 photoreduction stability with negligible loss after five consecutive cycles. Finally, a possible mechanism of CO 2 photoreduction using Pd/MgO/BiVO 4 was proposed for understanding the synergistic effects. The results of the experiment revealed that Pd/MgO/BiVO 4 can be a promising photocatalyst in solar energy conversion and storage application and can achieve excellent CO 2 photoreduction performance.
研究领域:
材料科学
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环境科学
·
能源科学
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2024
·
IF 8.4
Xi Chen,Zhenggang Wang,Zhuo Yang,Guozhen Liu,Guining Chen,Gongping Liu,Xiuxia Meng,Naitao Yang,Wanqin Jin
Towards natural gas purification , polymeric membranes generally face challenges of trade-off between permeability and selectivity , as well as CO 2 -induced plasticization effect. Previous works demonstrated that incorporating high-performing nanofillers and crosslinking the polymers are effective methods to overcome these two issues, respectively. In this work, we aimed to simultaneously improve permeability, selectivity and plasticization resistance of polymeric membranes by incorporating surface-engineered nanoporous fillers for CO 2 /CH 4 separation. DD3R zeolite nanoparticles with high purity were synthesized and then surface-functionalized by 3-aminopropyl trimethoxysilane (APTMS) to serve as the filler. Mixed-gas permeation measurements showed that DD3R zeolites offered CO 2 -selective channels in 6FDA-DAM polyimide based on molecular sieving effect of zeolitic aperture. 30 wt% DD3R-APTMS zeolite imparted the membrane with CO 2 permeability of 1661 Barrer (increased by 71.7%) and CO 2 /CH 4 selectivity of 28.0 (increased by 44.5%), which was beyond the upper-bound of polymeric membranes. Meanwhile, the hydrogen bond interaction between amino groups on APTMS and carboxyl groups on 6FDA-DAM rendered the resulting DD3R-APTMS MMMs highly enhanced plasticization resistance over 40 bar when equimolar CO 2 /CH 4 mixture as the feed. This work demonstrates a facile approach to simultaneously enhance separation performance and mitigate the plasticization effect.
研究领域:
材料科学
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化学工程
·
膜技术
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2018
·
IF 6.578
Leixin Yang,Shengbo Zhang,Hong Wu,Chumei Ye,Xu Liang,Shaofei Wang,Xingyu Wu,Yingzhen Wu,Yanxiong Ren,Yutao Liu,Nayab Nasir,Zhongyi Jiang
For high-performance mixed-matrix membranes (MMMs), it is crucial to design gas transport channels in fillers to rationally manipulate the structure-property relationship. In this study, the novel porous organosilicon nanotubes (PSiNTs) were incorporated into Pebax to prepare MMMs for biogas purification (CO 2 /CH 4 separation). After comparing the separation performance of MMMs containing PSiNTs and MMMs containing non-porous organosilicon nanotubes (SiNTs)，it can be found that the porous structure on wall of organosilicon nanotubes had a significant effect on the improvement of the gas permeability . In addition, the amino-modified PSiNTs (N-PSiNTs) were prepared and introduced into membranes to significantly enhance the CO 2 permeability and CO 2 /CH 4 selectivity. Firstly, the porosity of N-PSiNTs afforded rapid gas transport channels in MMMs and intensified the diffusion mechanism, increasing the CO 2 permeability. Secondly, the reversible reaction between amino groups and CO 2 in MMMs intensified the facilitated transport mechanism, increasing the CO 2 /CH 4 selectivity. In particular, the Pebax-N-PSiNTs with 0.5 wt% and 1 wt% N-PSiNTs exhibited the optimal separation performance, which surpassed 2008 upper bound and were superior to the MMMs incorporated with other kinds of nanotubes.
研究领域:
材料科学
·
环境工程
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Ying Cheng,Shumaila Razzaque,Zhen Zhan,Bien Tan
Fabrication of functionalized hypercrosslinked polymers (HCPs) with high specific surface area has gained significant research interest and their utilization for gas storage is still a trending research area. Considering the significance of solvent knitting strategy in construction of remarkably high surface area HCPs, we report fabrication of cyano-functional HCPs via one step Friedel-Crafts reaction. The series of HCPs were obtained by copolymerizing the rigid monomer TPB with a 2-napthonitrile in different molar ratio. The resultant co-polymerized polymers contained a plenty of nitrile functional groups and possessed high BET surface area. Among the series of such HCPs, HCP-TPB-CN-3:1 showed the highest BET surface area up to 2017 m 2 g −1 . These HCPs have enriched nitrogen in their pore walls that enhance the facile interaction of CO 2 to achieve higher capture capacity of 21.3 wt% at 273 K. Moreover, the HCP-TPB-CN was explored for CH 4 storage and showed absolute adsorption capacity of 0.35 g/g at 273 K, 80 bar, which is comparable with the porous polymers reported so far. These results highlight the significance of solvent knitting strategy and broaden the scope of HCPs for versatile industrial applications.
研究领域:
材料科学
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化学工程
·
环境科学
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高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2024
·Vol. 141
·期 16
·e55253
·
IF 2.7
Xiaocan Zhang,Siqin Zeng,Jiashu Long,Xuesong Li,Yutong Zhao
Using porous materials to selectively adsorb H 2 O from natural gas is a promising method to dehydrate methane (CH 4 ). The structure of a Zirconium metal-organic framework (Zr-MOF), namely, MIP-202, features a high density of amino groups, which can produce strong hydrogen bonding with H 2 O molecules. MIP-202 is cost-effective, green and scalable, and it exhibits good chemical stability under various conditions. This work incorporated MIP-202 nanoparticles into the high permeability polymer polyetherimide (PEI), and the obtained Mixed Matrix Membranes (MMMs) was used for the gas separation of H 2 O/CH 4 . It is found that MMMs loaded with 20 wt% of MIP-202 demonstrated a high H 2 O/CH 4 selectivity of 832.2, which was about 760 times of that of the pure PEI. This approach offers a new route to fabricate functional membranes for energy-efficient gas separations.
研究领域:
材料科学
·
环境工程
·
化学工程
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高影响因子
FUEL
·
2020
·
IF 5.578
Jing Bai,Xiang Zhen,Kele Yan,Pan Li,Shuqi Fang,Chun Chang
Lots of thermodynamics and kinetics accelerators have been used in the process of mixture gas separation by hydrate method, but there is still lack of valid screening method for seeking reliable and effective hydrate promoters. In this work, the effects of additive molecular diameter on the hydrate phase equilibrium condition and the quantity of hydrogen bond donor and accepter of additive on the separation efficiency during CO 2 (40.0 mol%)/CH 4 hydrate formation process were investigated. The results demonstrated that the larger molecular diameter of additive in cyclopentane (CP), tetrahydrofuran (THF) and tetrahydrothiophene (THT) systems, the phase equilibrium promotion effect of additive is more significant. And the empirical equations were proposed for predicting the phase equilibrium condition of CO 2 /CH 4 hydrate under the impact of additive with different molecular diameters. Moreover, on account of the quantity of hydrogen bond donor and acceptor of additive were different, the degree of mutual dissolution between additive molecule and aqueous solution was different, so that the number of additive molecules that could participate in the formation of hydrate was different, which had a certain impact on the separation efficiency.
研究领域:
化学工程
·
环境科学
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高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2026
·
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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高影响因子
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