Frontiers of Chemical Science and Engineering
·
2024
·Vol. 18
·期 4
·1-10
·
IF 4.3
Li Ying,Wang Lu,Xie Junyan,Dai Yong,Gu Xuehong,Wang Xuerui
Membrane gas separation is considered an energy-saving technique to extract He from natural gas due to no phase change and room temperature operation. However, the membrane performance was strongly limited by the trade-off between permeance and selectivity. Herein, novel 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)-2,2′-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (APAF)-5-amino-2-(4-aminobenzene) benzimidazole (BIA) asymmetric membranes with a thickness of 300 nm were successfully prepared by the non-solvent induced phase separation method. The membrane performance was modulated by regulating dope solution compositions (e.g., tetrahydrofuran and polymer concentration). The ideal He/CH 4 selectivity was 124 and the optimized He permeance reached 87 GPU, beyond the current upper bound. He/CH 4 selectivity was 75 and He permeance was 73 GPU for the binary mixture feed containing 0.2 mol % He. The membrane showed good resistance to CO 2 and C 2 H 6 , which are the typical impurities in natural gas. The 6FDA-APAF-BIA membranes have good stability (> 160 h), which can provide great potential in He extraction from natural gas.
研究领域:
膜科学
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气体分离
·
聚合物工程
·
相分离
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节能分离
·
材料科学
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高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2020
·
IF 4.551
Junjie Zhou,Hao Liu,Yichao Lin,Chen Zhou,Aisheng Huang
A well-shaped Ce (IV)-based metal organic framework (Ce-BDC) is prepared under solvothermal method. The influence of synthesis time, temperature and the amount of acetic acid (HAc) as a modulator is studied to develop a new strategy for the synthesis of well-shaped Ce-based MOF. The relationship between the synthesis parameters and morphology as well as crystallinity of Ce-BDC is investigated by XRD and SEM. Furthermore, the obtained well-shaped Ce-BDC shows a CO 2 uptake capacity of 2.28 mmol g −1 at 0 °C and 1.0 bar. Meanwhile, the breakthrough curve behaviors of Ce-BDC are investigated for a CO 2 /CH 4 and CO 2 /N 2 mixture gas . It is found that the Ce-based MOF adsorbs CO 2 under ambient temperature and pressure, but completely excludes CH 4 and N 2 , suggesting that it is a promising adsorbent for efficient separation of CO 2 from natural gas.
研究领域:
材料科学
·
无机化学
·
多孔材料
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气体分离
·
环境催化
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高影响因子
PETROLEUM CHEMISTRY
·
2025
·
IF 1.1
Jiang Ning,Mao Min,Wang Qingyin,Wang Gongying
MOF-5 is a classic metal-organic framework (MOF) crystal. However, synthesis of high-quality crystals usually requires an expensive N , N ′-diethylformamide (DEF) solvent, and a high molar ratio of a raw material (Zn 2+ : BDC 2– = 3‒5 : 1). More critically, its extreme instability against water vapor has caused researchers to do not use it. In this study, we achieved some important breakthroughs by using inexpensive N , N ′-dimethylformamide (DMF) solvent and meticulously optimizing synthesis parameters combined with a specialized micro-open solvothermal method. With a reduced molar ratio of a raw material (1.47 : 1), we successfully synthesized crystals exhibiting excellent phase structure and morphology, high surface area, out standing water vapor stability, and strong CO 2 adsorption capacity. The results show that the DEF replacement with DMF and reduction of the raw material molar ratio from 3 : 1 to 1.47 : 1 provides an increase of the BET surface area from ~935 to 2388 m 2 /g, and an improvement of the CO 2 adsorption capacity from ~0.8 to 2.5 mmol/g (298 K, 100 kPa). Breakthrough curves reveal that in simulated separation experiments for the flue gas and natural gas containing low CO 2 concentrations (10‒20%), the dynamic separation selectivity for CO 2 /N 2 reaches 22, while that for CO 2 /CH 4 remains stable at 4. Notably, the selectivity remained nearly unaffected by the pressure variation; this phenomenon is promising for enhancing the capture and purification of a low-concentration CO 2 from the flue gas and natural gas. It is important that the improved MOF-5 crystals prepared under optimal synthetic conditions maintained the stable phase structure and morphology even after 14-day exposure to humid air (relative humidity >70%), successfully overcoming the challenge posed by a water vapor.
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ENERGY & FUELS
·
2026
·
IF 6
Bin Zhou,Yi Zhang,Shugang Li,Zhen Wang,Haifei Lin,Yanlin Chen,Zeyou Meng,Haiqing Shuang,Liang Cheng,Qiqi Yin
The efficient separation of CH4 from binary CH4/N2 mixtures is crucial for utilizing low-concentration coalbed methane but remains a significant challenge. Herein, we systematically investigated the adsorption and separation performance of the metal–organic framework HKUST-1 for CH4, N2, and their mixed gases under different temperatures and pressures. Single-component adsorption experiments revealed that the adsorption capacity of HKUST-1 for CH4 was almost twice that of N2. The adsorption capacity of HKUST-1 for CH4 or N2 is negatively correlated with temperature, and there is a notably higher isosteric heat of adsorption for CH4 than for N2. In addition, grand canonical Monte Carlo (GCMC) simulations confirmed that both CH4 and N2 preferentially occupy the binding sites in T1 pores of HKUST-1 and then migrate to L2 and L3 pores. Differently, CH4 molecules form denser packing at the high-energy metal sites in HKUST-1, while N2 distributes more diffusely. The difference is due to the higher binding energy between CH4 and the Cu node (CH4 is −14.99 kJ/mol, while N2 is −7.83 kJ/mol). Leveraging ideal adsorbed solution theory (IAST) and a breakthrough curve, the superior adsorption selectivity of HKUST-1 for CH4 was evaluated in binary CH4/N2 mixtures. The total adsorption capacity of HKUST-1 for CH4/N2 mixtures is positively correlated with the CH4 concentration, and the adsorption selectivity is better at low CH4 concentrations or low temperatures. Meanwhile, HKUST-1 exhibits good moisture resistance and cycling stability. This research underscores the promise of HKUST-1 for efficient CH4/N2 separation and provides molecular-level insights for next-generation adsorbent design.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2026
·
IF 3.9
Zequn Li,Luogang Wu,Guangcan Huang,Xuetong Cui,Zilong Chen,Qiang Chen,Jian-Rong Li
Mixed matrix membranes (MMMs) incorporating metal–organic frameworks (MOFs) are attractive for molecular recognition and separations, but precisely engineering the MOF filler structure toward maximizing its inherent nanopore separation capability remains challenging. Here, we report a fluorination strategy to functionalize MIL-101 that synergistically optimizes its pore chemical environment and interfacial compatibility with the polymer matrix. Compared with the MIL-101/6FDA-DAM membrane, the incorporation of strong electron-withdrawing fluorinated ligands enhances both the CO2 adsorption affinity of MIL-101 and its hydrogen-bonding interaction with the 6FDA-DAM matrix. The optimized MIL-101-F/6FDA-DAM (10 wt %) membrane achieves a CO2 permeability of 2200 Barrer, a 150% enhancement over the pure 6FDA-DAM membrane, while maintaining a comparable CO2/CH4 selectivity of 21. The excellent separation performance surpasses the 2008 Robeson upper bound. This work provides a simple and effective approach to advancing the gas separation performance of MMMs.
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高影响因子
Nature Synthesis
·
2026
·
IF 22.6
Zhang Hao,Liu Ziming,Li Di,Wu Chenxin,Hua Lei,Li Haiyang,Yi Yanhui,Huang Rui,Yu Liang,Deng Dehui
Direct co-conversion of earth-abundant N 2 and CH 4 to high-value C–N–O compounds is a promising synthetic method but remains challenging, as the activation of N 2 and CH 4 typically requires high-energy conditions that can cause product decomposition. Here we report a plasma-cascade process for synthesizing cyclohexanone cyanohydrin (Cy(OH)CN) via direct coupling of N 2 and CH 4 plasma with cyclohexanone. This catalyst-free process achieves a Cy(OH)CN formation rate of 0.60 mmol h −1 with a high selectivity of 95.8% towards the cyclohexanone-derived products under mild conditions, concurrently generating ammonia as a valuable coproduct. Comprehensive mechanistic studies reveal that plasma-generated ·CH x and hydrogen radicals enable direct α-carbonyl functionalization of cyclohexanone to α-CH x cyclohexanol intermediates, which then coupled mainly with excited-state N 2 and are further activated by hydrogen radicals to generate Cy(OH)CN. This plasma-cascade strategy decouples the activation of inert molecules from the formation of relatively unstable C–N–O compounds, enabling selective cyanohydrin synthesis that avoids using high-cost NH 3 and toxic HCN. The alternative text for this image may have been generated using AI.
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高影响因子
Processes
·
2026
·Vol. 14
·期 13
·2072
·
IF 3.4
Tao Wei,Shibing Cai,Liangning Huang,Jianwei Song,Tu Hu,Huanwu Zhan
Methane (CH4) was employed as a carbon source for the reduction and carburization of TiO2via a gas-phase infiltration process to synthesize titanium carbide (TiC). The highly reactive and diffusible carbon species derived from CH4decomposition enable a significant reduction in both reaction time and temperature compared with conventional carbothermal reduction methods. The phase evolution during the CH4-driven reduction–carburization of TiO2was analyzed, and the effects of CH4volume fraction, reaction temperature, and reaction time on the carburization efficiency were systematically investigated, with the phase composition and microstructure of the products also characterized. The optimal conditions in a CH4-Ar system were found to be 10%CH4–90%Ar at 1270 °C for 8 h, yielding a carburization efficiency of 79.1% for TiO2pellets. Increasing the CH4proportion led to more severe carbon deposition, with deposited carbon adhering to the pellet surface and clogging the internal pores. Raising the temperature promoted the reduction–carburization reaction, but excessive acceleration of CH4cracking above 1270 °C caused carbon accumulation on the TiO2surface, forming a carbon shell that lowered the carburization efficiency. Prolonging the reaction time was beneficial for achieving a higher degree of carburization.
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Journal of Environmental Chemical Engineering
·
2026
·Vol. 14
·期 4
·123279
·
IF 7.5
Bolin Chen,Chunhong Nie,Nan Yang,Wen Xin,Zhichao Gong,Luhua Hou,Haonan Zhang
Solar-driven carbon dioxide reduction (CO 2 RR) is a highly promising strategy for closing the carbon cycle and enabling the sustainable production of clean chemicals. However, its practical efficiency remains severely limited by sluggish reaction kinetics and competing reaction pathways. In this study, through rational interfacial engineering to induce a stable built-in electric field, we constructed an S-scheme heterojunction based on CeO 2 (110)/g-C 3 N 4 to achieve coordinated modulation of photocatalytic CO 2 reduction. Under gas-solid-phase reaction conditions without a sacrificial agent, the catalyst delivered a yield of 2.51 μmol·g −1 ·h −1 , representing an 8.05-fold enhancement compared with pristine g-C 3 N 4 . A series of experimental investigations indicate that the internal electric field not only promotes the efficient separation and migration of photogenerated carriers but also strengthens CO 2 adsorption and activation, thereby steering the original CO-forming pathway toward an eight-electron-dominated CH 4 pathway. This work may offer a viable heterojunction design strategy for achieving selective CO 2 RR.
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高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2026
·
IF 5.4
Jingli Zhai,Wanting Li,Xinyu Zhang,Qian Zhang,Xiaoqiang Liu,Ruifeng Chong,Caixia Feng,Yan Wang,Danny K.Y. Wong,Yanmei Zhou
Herein, a bimetallic zinc-cobalt metal-organic framework (ZnCoMOF) microsphere cluster with abundant oxygen vacancies was rationally designed and synthesized for visible-light-driven photocatalytic CO 2 reduction. XPS results reveal that the substitution of Co 3 + by Zn 2+ modulated the electronic structure of Co sites, reduced the Co 3+ /Co 2+ ratio, and generated electron-rich Co 2+ centers as well as oxygen vacancies. The reversible Co 3+ /Co 2+ redox pair accelerates charge migration, while oxygen vacancies inhibit carrier recombination. Moreover, electron-enriched Co 2+ favor CO 2 activation. The synergistic effect of multiple active centers optimizes reaction kinetics and catalytic performance. The optimized Zn 0.3 Co 1 MOF delivered a CO yield 2.21 times as high as that of pristine CoMOF, reaching 5.33 mmol g −1 within 4 h, and it achieved an ultrahigh CO selectivity of 100%. The enhanced performance benefits from Zn-induced electronic modulation and synergistic catalysis. Notably, in a diluted CO 2 atmosphere, the product composition exhibits an obvious transition from CO to CH 4 with the decrease in CO 2 concentration. Lower CO 2 concentration contributes to a higher CH 4 yield and greater CH 4 selectivity in the products. Under 20% CO 2 atmosphere, the CH 4 production reached 0.36 mmol g −1 within 4 h with an ultra-high CH 4 selectivity of 100%. These results indicate that in the Zn x Co 1 MOF-catalyzed CO 2 reduction system, product selectivity can be readily modulated by adjusting CO 2 concentration. This offers a facile strategy for the efficient utilization of low-concentration CO 2 from industrial flue gas. Download: Download high-res image (394KB) Download: Download full-size image
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Catalysts
·
2025
·Vol. 15
·期 7
·623
·
IF 4
Caidong Du,Wenwei Wu,Jiangtao Shang,Keyi Xiang
Methane (CH4) has attracted much attention regarding its use in electrochemical carbon dioxide reduction reaction (CO2RR) due to its high mass-energy density; however, the uneven adsorption of intermediates on copper sites by conventional Cu-based catalysts limits the selective production of CH4. The introduction of a second metal can effectively regulate the adsorption energy of intermediates on the Cu site. In this paper, a method of alloying Cu with oxyphilic metals (M) using rapid electrodeposition is presented; the synergistic effect of the bimetal effectively directed the reaction pathway toward CH4. The best Faraday efficiency for methane occurred in the optimized Cu30La20electrode, reaching 66.9% at −1.7 V vs. RHE potential. In situ infrared testing revealed that the *CHO intermediate—a critical species for the electrocatalytic conversion of CO2to CH4—was detected on the Cu30La20catalytic electrode. However, no *CHO intermediate was observed on the Cu20La30electrode. Instead, the characteristic peak of the *OCCHO intermediate associated with C-C coupling emerged on the Cu20La30catalyst. This indicates that the adsorbed oxygen-containing groups on lanthanum sites reacted with carbon-containing groups on copper sites to form C2products, serving as the primary reason for the shift in reduction products from methane to ethylene.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Cancan Yang,Yugao Wang,Jiaxin Jing,Linyuyang Shi,Jinping Li,Jiangfeng Yang
Activated carbon (AC) is a commonly used and readily available adsorbent for CH 4 and N 2 adsorption separation, however, it is seriously hindered by the uneven micropore size distribution of AC and inappropriate microporous size. In this work, a commercial AC was modified with CuCl 2 for addressing the limitation and thereby enhancing CH 4 /N 2 adsorption separation performance. According to in-situ X-ray diffraction analysis, Cu species were volatilized in the form of CuCl functioning as a dynamic porogen during thermal treatment. The process homogenized the initially irregular and broad pore size distribution of the original AC, which accounted for enhancing CH 4 /N 2 adsorption separation selectivity from 4.44 to 7.53. This investigation provides a powerful and potential modification approach for enhancing CH 4 /N 2 adsorption separation performance of the commercial AC.
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MOLECULES
·
2025
·Vol. 30
·期 13
·2691
·
IF 4.6
Jiuhu Zhao,Jingjing Jiang,Guanyu Chen,Meng Wang,Xiaoyuan Zuo,Yanjiao Bi,Rongshu Zhu
The selective catalytic reduction of NOxwith CH4(CH4-SCR) holds the potential to simultaneously abate harmful NOxand CH4greenhouse gases. In this study, a series of bimetallic M-In/H-SSZ-39 catalysts (where M represents Cr, Co, Ce, and Fe) were prepared via an ion exchange method and subsequently evaluated for their CH4-SCR activity. The influences of the preparation parameters, including the metal ion concentration and calcination temperature, as well as the operating conditions, such as the CH4/NO ratio, O2concentration, water vapor content, and gas hourly space velocity (GHSV), on the catalytic activity of the optimal Cr-In/H-SSZ-39 catalyst were meticulously examined. The results revealed that the Cr-In/H-SSZ-39 catalyst exhibited peak CH4-SCR catalytic performance when the Cr(NO3)3concentration was 0.0075 M, the In(NO3)3concentration was 0.066 M, and the calcination temperature was 500 °C. Under optimal operating conditions, namely GHSV of 10,000 h−1, 400 ppm NO, 800 ppm CH4, 15 vol% O2, and 6 vol% H2O, the NOxconversion rate reached 93.4%. To shed light on the excellent performance of Cr-In/H-SSZ-39 under humid conditions, a comparative analysis of the crystalline phase, chemical composition, pore structure, surface chemical state, surface acidity, and redox properties of Cr-In/H-SSZ-39 and In/H-SSZ-39 was conducted. The characterization results indicated that the incorporation of Cr into In/H-SSZ-39 enhanced its acidity and also facilitated the generation of InO+active species, which promoted the oxidation of NO and the activation of CH4, respectively. A synergistic effect was observed between Cr and In species, which significantly improved the redox properties of the catalyst. Consequently, the activated CH4could further interact with InO+to produce carbon-containing intermediates such as HCOO−, which ultimately reacted with nitrate-based intermediates to yield N2, CO2, and H2O.
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PubMed
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