MICROPOROUS AND MESOPOROUS MATERIALS
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2025
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IF 4.7
Xiaoxia Zhang,Congmei Chen,Meng Rong
The development of advanced microporous organic polymers with high CO 2 capture efficiency and efficient removal of toxic volatile organic compounds under high-humidity conditions remains a significant challenge. In this work, three highly hydrophobic fluorinated tetraphenyladamantyl microporous organic polymers (FMOPs) were fabricated via C – H arylation of 1,3,5,7-tetra(4-bromophenyl)adamantane with 1,2,4,5-tetrafluorobenzene, 1,2,4,6-tetrafluorobenzene, and 1,3,5-trifluorobenzene, respectively. The effects of fluoroaromatic linking units on the porosity, chemical properties, static and dynamic gas/vapor adsorption performance under dry and high humidity conditions were systematically investigated. It was found that fluoroaromatic linkers with isomerism and higher functionality facilitate the formation of highly porous network. The fluorinated FMOPs demonstrated strong hydrophobicity with minimal water vapor adsorption (0.06–0.17 wt%, 298 K/0.9 P/P 0 ). Among them, FMOP-3 exhibited the highest BET surface areas of 1373 m 2 /g and a narrow pore size distribution (0.55 nm and 0.93 nm). FMOP-3 also showed remarkable CO 2 uptake (12.2 wt%, 273 K/1.0 bar) and CO 2 /N 2 selectivity (46.4). Notably, the FMOPs simultaneously possess exceptional adsorption capacities for benzene (122.5-149.6 wt%) and cyclohexane (95.3-122.8 wt%), significantly surpassing most previously reported porous organic polymers. Moreover, dynamic breakthrough experiments under high humidity (85% RH) confirmed the high capture efficiency of FMOPs. Experimental characterizations and theoretical calculations confirmed that fluorination enhances the interactions of CO 2 @FMOPs and benzene@FMOPs through dipole–quadrupole interactions and fluorine-induced strengthened π-π interactions. These findings highlight the potential of FMOPs for highly efficient CO 2 capture and toxic volatile organic vapor removal under high-humidity conditions. In addition, this work also provides some insights into developing advanced functional adsorbents for gas molecule capture under high-humidity conditions.
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Journal of CO2 Utilization
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2024
·
IF 7.2
Xinjuan Li,Yan Liu,Ao Li,Xuening Ma,Xianbin Jia,Yahao Dong
Constructing stable nanochannels and nanoconfined environments for ionic liquids holds significant application value in gas separation, ion channels, and related fields. The functional polyionic liquid synthesized in this study exhibits a controllable assembly structure and demonstrates liquid crystal properties. Through heating and water treatment, the polyionic liquids crosslink to form multi-hierarchical nanopores, including sub-nanochannels with pore sizes similar to CO 2 , without the need for a catalyst. The specific surface area and pore size of the polyionic liquid network (PILC) were adjusted by regulating the self-assembly of polyionic liquids in water. The unique PILC, combining ionic liquid nanopores and liquid crystal structure properties, shows high CO 2 adsorption performance and excellent CO 2 /N 2 selectivities, surpassing commonly reported ionic liquid porous materials. Furthermore, PILC-2 exhibits good catalytic performance for CO 2 cycloaddition, and its catalytic activity and selectivity did not significantly decrease after five cycles. This study successfully introduces hierarchical ionic liquid nanochannels into porous networks without involving any inorganic ordered nanomaterials. This provides a simple and effective approach for the highly selective adsorption and separation of CO 2 , as well as for the preparation of catalytic materials.
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ACS Catalysis
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2025
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IF 13.1
Yang Chen,Diwen Zhou,Yongli Chang,Yunzhao Xu,Hongqiao Lin,Lizhi Wu,Yu Tang,Chengyi Dai,Xingang Li,Lisheng Guo,Ting Qiu,Li Tan
The utilization of Rh-based catalysts in the direct production of ethanol from CO2 has been a subject of significant interest. However, to date, the precise active sites responsible for ethanol generation and the C–C coupling mechanism remain elusive. In this study, we present a Rh-based catalyst featuring nanoscale Rh–Fe alloy sites, which achieved an ethanol selectivity of 49.1% among all hydrocarbon and oxygenate products (CO excluded) under relatively mild reaction conditions (3.0 MPa, 200 °C, with a low metal loading of ≤1 wt %). The formation of ethanol proceeds via the HCOO* pathway with a CO insertion mechanism occurring at the alloy sites with a specific cluster size, where CH2* and CO* act as the crucial intermediates for C–C coupling. The electron interaction within the Rh–Fe alloy sites effectively reduces the energy barrier for the formation of the CH2CO* intermediate, thereby facilitating the production of ethanol. In contrast to the Rh–Fe alloy sites, the geminal-dicarbonyl binding configuration of CO* intermediates on Rh single sites favors the generation of byproducts such as methane and methanol, rather than ethanol. This research offers insights into the active sites and reaction mechanism of hydrogenation of CO2 to ethanol, thus enhancing the efficient utilization of Rh-based catalysts.
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Industrial Chemistry & Materials
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2025
·
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.
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ELECTROCHIMICA ACTA
·
2025
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IF 5.6
Yadan Yu,Wenyu Li,Huiting Qiao,Yuyu Liu,Momo Safari,Haitao Huang,Jinli Qiao
CO 2 electroreduction enables the sustainable conversion of greenhouse gases into value-added chemicals, thereby reducing global warming. In this study, a bismuth–samarium (Bi–Sm) bimetallic catalyst (Bi 4 Sm 1 ) was prepared, exhibiting excellent performance for the CO₂-to-formate electrosynthesis facilitated by situ-generated nanosheets. The incorporation of Sm into Bi catalyst enriched the active sites on the catalyst surface, achieving excellent stability (>150 h) and high formate selectivity (Faradaic efficiency, FE formate = 93.74%) with a current density of 13.5 mA cm -2 at −1.0 V vs. reversible hydrogen electrode (V RHE ) in a H-cell reactor containing 0.5 M KHCO 3 electrolyte. Moreover, in a flow cell containing 1M KOH electrolyte, the catalyst achieved a current density exceeding 162 mA cm -2 at -0.7 V RHE , with a slight decrease in FE formate (92.55%). This catalyst outperformed most reported catalysts, highlighting its large-scale potential applications.
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GREEN CHEMISTRY
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2025
·
IF 9.2
Xianda Zhang,Yaotian Yan,Yangshuo Liu,Chun Li,Jian Cao,Junlei Qi
CO2 reduction reaction (CO2RR) has been considered as a promising process that can compensate CO2 emission and convert it into value-added chemicals. In preparation of CO2RR catalytic electrode, Nafion is a common binder but its effect in catalytic process is usually ignored. Herein, we proposed the bifunction of Nafion in CO2RR based on its molecular structure and successfully developed a CO2-affinitive surface of Micro-Ag /Nafion by controlling the content of Nafion, which exhibited a superior CO faradaic efficiency (FECO) of 95.07% at -0.9 V (vs. RHE). This excellent FECO and 2 times of CO partial current density (jCO) in flow-cell proved its industrial prospect. Its splendid selectivity of CO2RR was attributed to the selective polarization of CO2 molecule at Nafion, which resulted in the 6.8 times higher adsorption energy (Eads) of CO2 than H2O. Therefore, CO2RR gained an advantage in the competitive reaction.Nafion was recognized as a favorable transporter for CO2 on the surface of metal catalyst. Our work describes the bifunctional role of Nafion in CO2RR electrode and it will contribute to optimize the design of metal/Nafion catalytic material for CO2RR.
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ACS Sustainable Chemistry & Engineering
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2025
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IF 7.3
Chongyang Wei,Yidan Wang,Haoting Liang,Ting Li,Jing Lv,Mei-Yan Wang,Yue Wang,Shouying Huang,Xinbin Ma
Direct conversion of CO2 to aromatics has received considerable attention as a typical CO2 utilization technology for mitigating climate change. Efficiently regulating the distribution of aromatics remains a significant challenge. Here, we report on a series of bifunctional catalysts composed of Na/Fe and Ni/ZSM-5 zeolites with varying Ni content, which achieve a controlled distribution of aromatics in direct CO2 hydrogenation to aromatics. The hydrogen spillover effect of Ni on ZSM-5 accelerates the cracking of aromatics and consequently increases the BTX (benzene, toluene, xylene) content in the aromatics to as much as 78.4% (mol %). Ethylbenzene dealkylation as a model reaction reveals that introduction of Ni facilitates the removal of branched chains from aromatics in the form of CH4, leading to a positive correlation between CH4 selectivity and the BTX ratio in aromatics with the amount of spillover hydrogen. The hydrogen spillover effect also significantly reduced the coke content on HZSM-5, prolonging the catalyst life. However, excessive hydrogen spillover increases the hydrogen coverage on Fe species, inhibiting the carburization of Fe, which is unfavorable for CO2 conversion. These insights offer a new strategy for controlling the distribution of aromatics over bifunctional catalysts over the conversion of C1 to aromatics.
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SEPARATION AND PURIFICATION TECHNOLOGY
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2025
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IF 9
Ruqing Chong,Xiangyan Dou,Zhaoqi Deng,Zhangzhou Luo,Zihui Meng,Wenfang Liu
With formate dehydrogenase (FDH) as the biocatalyst and reduced nicotinamide adenine dinucleotide (NADH) as the cofactor, enzyme catalysis achieves high-selectivity CO 2 reduction to formic acid under ambient conditions. However, this route relies on susceptible and costly enzyme and cofactor, and faces difficulties in their recovery and reuse. Enzyme immobilization and cofactor regeneration are essential strategies to address these issues. Herein we designed a dual-function Ti 3 C 2 T x /graphene (GA)/TiO 2 (TGT) composite aerogel, after amino modification, FDH was immobilized on the aerogel via glutaraldehyde chemistry. Then it was innovatively applied in a photo-enzyme coupled system (PECS) that mimics natural photosynthesis and engenders sustainable CO 2 reduction by integrating photocatalytic NADH regeneration with enzymatic CO 2 reduction. Porous GA aerogel not only enables high specific surface area that facilitates enzyme immobilization and substrate adsorption, but also extends the light response of TiO 2 from ultraviolet to visible light range and reduces band gap. Ti 3 C 2 T x contributes simultaneously to photocatalysis and enzyme reaction through its excellent electronic conductivity, large two-dimension surface and good CO 2 affinity. Ultimately, TGT demonstrated photocatalytic activity of 58.8 μM/(g·min) and NADH yield of 14.9 %. TGT immobilized FDH exhibited an enzyme activity recovery of 81.4 % and produced 0.24 mM formate. With 2 mM cofactor, formate yield reached 12.4 % in the PECS, surpassing most reported systems.
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MOLECULES
·
2025
·Vol. 30
·期 12
·2626
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IF 4.6
Minhui Pan,Linlin Zheng,Congyu Cai,Weiwei Wang
The photocatalytic reduction of CO2into valuable hydrocarbons presents significant potential. In this research, a ZnO/ZnAl2O4composite photocatalyst was synthesized using the hydrothermal method, resulting in a marked enhancement in CO yield—approximately three times greater than that achieved with pure ZnAl2O4nanoparticles. The formation of a Z-scheme heterojunction between ZnO and ZnAl2O4was observed, characterized by low interfacial charge transfer resistance, an abundance of reaction sites, and optimized charge transport pathways. Within this composite, ZnO contributes additional vacancies, thereby increasing active sites and enhancing the separation and migration of photogenerated carriers. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis indicates that ZnAl2O4facilitates the formation of key intermediates, such as *COOH and HCO3−, thus promoting the conversion of CO2to CO. This study offers valuable insights into the design of heterogeneous catalysts with diverse active components to enhance the performance of CO2photocatalytic reduction through synergistic effects.
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PubMed
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Processes
·
2025
·Vol. 13
·期 9
·2903
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IF 2.8
Ping Guo,Yong Li,Yanbao Liu,Yunlong Zou
In this study, a new type of double crosslinked nanospheres (DCNPM-A) was developed to solve the problem of gas channeling caused by fracture development in the process of CO2oil displacement, and the microsphere system with delayed swelling was successfully synthesized by inverse micro lotion polymerization. The microsphere adopts a dual crosslinking structure of stable crosslinking agent (MBA) and unstable crosslinking agent (UCA), achieving intelligent sealing function of shallow low expansion and deep high temperature triggered secondary expansion. The successful preparation of microspheres was verified by characterization methods such as Zeta potential and SEM, and the effects of reaction temperature, time, initiator and crosslinking agent dosage on microsphere properties were systematically studied. The experimental results show that DCNPM-A microspheres exhibit excellent expansion performance, thermal stability, and acid resistance in acidic, high-temperature, and high mineralization environments. Their expansion ratio can reach 13.5 times, and they can maintain stability for more than 60 days in supercritical CO2environments. Core displacement experiments have confirmed that the microspheres have the best sealing performance in matrices with a permeability of 10 × 10−3μm2and fractures with a width of 0.03 mm. The combination of 0.8 PV injection volume, 0.5 mL·min−1injection rate, and continuous injection method significantly improved the plugging rate and recovery rate of CO2flooding. This study provides new technical support for the efficient development of low-permeability fractured reservoirs.
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JOURNAL OF MEMBRANE SCIENCE
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2025
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IF 9
Qingnan Wang,Yanting Tang,Longjie Liu,Chenlu Liu,Keming Zhang,Xiaohe Tian,Xiaoting Feng,Rui Zhang,Yueyangchao Yu,Tianhe Gu,Bin Liu,Shaofei Wang
The scalable fabrication of large-area, defect-free metal-organic framework (MOF) membranes for precise gas separation is hindered by their intrinsic brittleness and polycrystalline defects. Herein, we present a molecular weaving strategy to construct an interwoven mixed matrix membrane of rigid 3D UiO-66 gel and flexible polyethyleneimine (PEI) polymers, achieving both structural robustness and tunable porosity. Glutaraldehyde crosslinking further stabilizes the hybrid framework, enhancing mechanical durability while refining pore dimensions to 0.35 nm, ideal for H 2 /CO 2 sieving. The resultant ultrathin (∼50 nm) but flexible membranes, with UiO-66 content up to 46 wt%, exhibit superior separation performance, achieving a H 2 permeance of 845 GPU and H 2 /CO 2 selectivity of 16.8, surpassing the 2008 Robeson upper bound. Additionally, we demonstrated the fabrication of defect-free membranes ∼160 cm 2 , showcasing the scalable potential of this method. This work introduces a promising strategy for designing flexible, high-performance MOF-based separation systems, addressing urgent challenges in energy-efficient gas purification and carbon capture.
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CHEMICAL ENGINEERING JOURNAL
·
2025
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IF 13.2
Hang Zhou,Xiaomeng You,Zejiang Huang,Beibei Xu,Yingli Shi,Xuelu Wang,Ye-Feng Yao
Dual-atom catalysts, which combine the strengths of single-atom catalysts and metal alloys, are considered optimal for facilitating electrocatalytic CO 2 reduction processes. However, developing the means of enhancing the utilization efficiency of bimetallic atoms at catalytic sites and controlling the complex atomic coordination environment to achieve high selectivity and Faradaic efficiency remain a challenge. The present work addresses this issue by synthesizing a bimetallic SnCu-WC x catalyst via the introduction of individual Sn and Cu atoms supported on a tungsten carbide substrate. High Faradaic efficiencies of 98.62 % and 90.19 % at current densities of 100 and 500 mA cm −2 for the reduction of CO 2 to formate are respectively achieved through modulation of the coordination environment and electron/proton transfer during catalysis, the creation of shared adsorption sites, and the promotion of synergistic electrocatalysis. The results of operando nuclear magnetic resonance spectroscopy indicate that activated *OH groups are involved in the formation of formate due to the affinity of individual Sn atoms in the SnCu-WC x catalyst toward *OH. Density functional theory calculations confirm that the presence of individual Sn atoms in SnCu-WC x promotes the dissociation of H 2 O, and thereby modulates the catalytic microenvironment to accelerate the kinetics for the conversion of activated *CO to *COOH groups. Accordingly, the proposed strategy offers new insights into the design of bimetallic catalysts.
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