LANGMUIR
·
2023
·
IF 3.9
Zhen Zhao,Lu Zhang,Hao Zhang,Guoqiang Lu,Tong Meng,Hongguo Hao,Yongmin Zhang,Jun Li,Hui Yan
The superamphiphiles exhibit broad prospects for fabricating stimuli-responsive emulsions. Because the superamphiphiles are assembled via noncovalent interactions, they have the advantage of fast response and high efficiency. Recently, a series of switchable emulsions using CO2-responsive superamphiphiles have been developed, which extends the applications of CO2-responsive materials in widespread field. However, there is still a lack of fundamental understanding on the switching mechanism related to the assembled structure of superamphiphiles at the oil–water interface. We employed molecular dynamics (MD) simulations to investigate the reversible emulsification/demulsification process of a responsive emulsion system stabilized by a recently developed responsive superamphiphile (BTOA), which consists of oleic acid (OA) and cationic amine (named 1,3-bis(aminopropyl)tetramethyldisiloxane, BT). The simulation results present the morphologies in both the emulsion and demulsification states. It is found that the ionized OA– and the protonated BT+ together form an adsorption layer at the oil–water interface. The hydrophobic parts of BT+ are inserted into the adsorption layer, and the two amine groups contact the water phase. This adsorption layer reduces the interfacial tension and stabilizes the emulsion. After the bubbling of CO2, the surfactants were fully protonated to OA and BT2+. Because of the changes in the molecular polarity, OA and BT2+ entered the oil and water phases, respectively, resulting in demulsification. The structural and dynamical properties were analyzed to reveal the different intermolecular interactions that were responsible for the reversible reversibility of the emulsion. The observations are considered to be complementary to experimental studies and are expected to provide deeper insights into studies on developing responsive materials via supramolecular assemblies.
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高影响因子
AICHE JOURNAL
·
2023
·Vol. 70
·期 4
·e18349
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IF 3.7
Youluan Lu,Haonan Wu,Dongna Li,Yi Huang,Huijuan Guo,Tielin Wang,Lijuan Shi,Qun Yi
Porous frustrated Lewis pairs (FLPs) have been demonstrated as cutting-edge heterogeneous catalysts in acidic–basic catalysis, which, yet faces great challenges in synthesis. Herein, we propose a one-step de novo assembly strategy for constructing porous FLPs by capping monodentate ionic liquids (ILs) on metal clusters during the synthesis of metal–organic frameworks (MOFs). The capping of ILs makes adjacent metal sites on MOFs transforming to coordinatively-unsaturated metal Lewis acids, producing FLPs containing Lewis basic Cl − ions from ILs and metal sites. The distribution of ILs on the framework of MOFs endows the catalysts with large surface areas (up to 2125 m 2 g −1 ), open channels and good stability. The porous FLPs behave unprecedented activity for atmospheric CO 2 activation and coupling with epoxides (25–40°C, 1 bar, without cocatalyst). This de novo assembly strategy exhibits good universality for synthesizing porous FLPs from different kinds of ILs, paving a facile approach for designing high-efficiency acidic–basic catalysts.
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ENERGY & FUELS
·
2023
·
IF 5.3
Tongxin Li,Xuefei An,Jiaqi Chen,Long Fan,Dong Fu
CO2 capture and storage (CCS) from point sources is an important part of CO2 emission reduction technologies. In particular, adsorbents with high capacity and selectivity are needed to reduce the cost of CCS technologies. Herein, we report the controlled synthesis of N-doped carbon materials, which exhibit high CO2/N2 selectivity and CO2 adsorption capacity. Specifically, cellulose-based nitrogen-doped carbon aerogels (CNCAs) were prepared using cellulose as a precursor and dissolving it in the mixed solution of NaOH and urea, followed by hydrothermal polymerization, freeze-drying, carbonization and activation. During the experiment, the effects of NaOH and urea on the formation and microstructure of carbon aerogels (CAs) were tested, and the impacts of carbonization/activation temperature on the pore structure, nitrogen content, microcrystalline structure and CO2 adsorption performance were further investigated. Impressively, for a simulated flue gas with a composition of 15% vol of CO2 and 85% vol of N2, the CNCA-750 adsorbent prepared in this work showed excellent adsorption and separation performance for CO2. The adsorption capacity can reach 3.65 mmol CO2/g and that selectivity can reach 19.69. Compared with other absorbents, it has excellent water resistance, high chemical stability, low cost and lower adsorption heat. Comprehensively, CNCAs have great prospects in the ultralow emission of industrial flue gas.
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Nanomaterials
·
2023
·Vol. 13
·期 24
·3153
·
IF 5.3
Zhenteng Sheng,Hui Zhou,Yuhua Zhang,Jinlin Li,Li Wang
The selective hydrogenation of CO2into high-value chemicals is an effective approach to address environmental issues. Cobalt-based catalysts have significant potential in CO2hydrogenation reaction systems; however, there is a need to control their selectivity better. In this study, copper is introduced onto Co3O4nanosheets using the ion exchange reverse loading method. The unique interaction of these materials significantly alters the selectivity of the cobalt-based catalyst. Results from scanning transmission electron microscopy and scanning electron microscopy indicate that this catalyst enables a more even dispersion of copper species in the Co3O4nanosheets. Temperature-programmed reduction and X-ray photoelectron spectroscopy reveal that the catalyst facilitates the metal–metal interaction between Co and Cu. Temperature-programmed desorption experiments for CO2and H2demonstrate that the close interaction between Co and Cu modifies CO2adsorption, leading to differences in catalytic activity. Moreover, the catalyst effectively suppresses CO2methanation and promotes methanol formation by altering the alkalinity of the catalyst surface and weakening the hydrogen dissociation ability.Keywords:CO2hydrogenation;methanol;cobalt;copper
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Zhen-Jie Yu,Hao-Nan Li,Kexin Man,Jia-Hui Xin,Chao Zhang,Zhi-Kang Xu
Holey graphene oxide nanosheets enables uniform hydrogel filling in lamellar membranes • Metal ions densify gel network to increase selectivity and facilitate CO 2 transport • Zn 2+ balances CO 2 adsorption and desorption for rapid transport • Optimized membranes achieve CO 2 permeance of 27 GPU and CO 2 /CH 4 selectivity of 142 • The metal-ion regulation strategy demonstrates general applicability Exploiting efficient CO 2 /CH 4 separation membranes has emerged as indispensable platform for natural gas upgrading. Two-dimensional lamellar membranes offer immense opportunities in boosting CO 2 /CH 4 separation performance by introducing polar groups as facilitated transport carriers capable of forming strong interactions with CO 2 . Nevertheless, these lamellar membranes are largely restricted by inferior CO 2 /CH 4 selectivity of below 100, owing to the lack of efficient facilitated transport carriers to distinguish comparable kinetic diameter and polarizability of two gases. Herein, we bypass conventional carriers and discover a powerful and universal transition metal ion-modulated strategy to formulate holey graphene oxide/hydrogel lamellar membranes, rendering exceptional CO 2 /CH 4 selectivity over previously-reported lamellar membranes. In our strategy, transition metal ions play dual functions: performing high-efficient and tailorable CO 2 carriers via π-complexation for sustaining rapid permeance; and densifying hydrogel network within nanochannels via coordination for improving selectivity. By regulating the type and concentration of transition metal ions, our lamellar membranes yield a considerable CO 2 permeance of 27 GPU and a superior CO 2 /CH 4 selectivity of 142, which is about 3.7-folds of that without transition metal ions. This approach is broadly applicable to various metal ions, offering a paradigm shift in exploiting new lamellar membranes towards specific gas separation and beyond. Download: Download high-res image (187KB) Download: Download full-size image
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CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Hanzi Liu,Xinlin Xie,Lei Liu,Zhigang Yi,Xing Peng,Pansong Li,Zhiqiang Sun
Solid-phase DFMs yielded 0.65 mmol g −1 CH 3 OH in ICCU at 300 °C and 30 bar. • Ga promoted methanol production by optimizing the Cu-ZnO x interface. • Cu-ZnO x promoted CO 2 migration and activation for CH 3 OH synthesis. • DFT, AIMD, and DRIFTS revealed formate hydrogenation pathways. • Cu-ZnO x interfaces enable ZnO to Cu electron transfer, lowering barriers by 0.51 eV. The development of dual functional materials (DFMs) for cyclic CO 2 capture and hydrogenation is essential for converting diluted CO 2 into valuable C 1 products, yet remains challenging due to inherent trade-off between CO 2 conversion and CH 3 OH selectivity over catalysis center. Herein, we engineered a series of copper-based materials and for selective hydrogenation of CO 2 to CH 3 OH. The highly dispersed Cu-ZnO-Ga catalyst demonstrated exceptional methanol formation activity of 0.65 mmol g −1 at 300 °C and 30 bar in 1 h hydrogenation time. Through a quantitative investigation of coordination environments, we revealed that pressure-induced conditions promote Cu 0 nanoparticle migration toward ZnO x species, generating synergistic Cu 0 -Zn δ+ interfacial sites. These interfaces facilitated CO 2 activation via a deoxygenation pathway, while carbonates remain inert during hydrogenation. Combined in situ spectroscopy and theoretical calculations demonstrated that stable formate and methoxy intermediates on Cu 0 -ZnO x facilitated heterolytic C O scission and C H bonding, significantly lowering the energy barrier for activating captured CO 2 .
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MACROMOLECULES
·
2023
·
IF 5.5
Ke Wang,Jialu Zhang,Meiyu Si,Zilong Wang,Liru An,Guiyan Liu,Yongfei Zeng
A series of temperature/pH/CO2/redox-quadruple-responsive ferrocene-containing homopolymers were prepared for the first time. These homopolymers contain hydrophilic ethoxy group, amino group, and hydrophobic ferrocene (Fc) and were synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. They showed four different stimuli responses. (1) They exhibit an upper critical solution temperature (UCST) in n-propyl alcohol and n-butanol, which can be adjusted by the molecular structure, molecular weight, and concentration. (2) They have a critical pH in aqueous solution and are affected by molecular structure, molecular weight, and concentration. (3) The CO2 response of the homopolymers was confirmed by cyclic bubbling CO2/N2 to the solution. (4) The redox response of homopolymers was demonstrated by adding a chemical oxidant (FeCl3)/reductant (VC) or electrical stimulation to the solution of homopolymers. In addition, these homopolymers are amphiphilic, and their self-assembly behavior in solution was investigated. It was found that they have different critical micelle concentrations (cmc) and can form lamella, sphere, and agglomerated sphere in solution, and the morphology can be reversibly changed by applying stimulation. Finally, the release behavior of micelles of the homopolymer was explored by wrapping Nile Red (NR), which proved that they had good release efficiency. These temperature/pH/CO2/redox-quadruple-responsive ferrocene-containing homopolymers expand the types of multistimuli-responsive homopolymers and have excellent application prospects in the fields of self-assembly, drug delivery, and electrode materials.
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Materials
·
2023
·Vol. 16
·期 21
·7042
·
IF 3.4
Shuling Shen,Xuecong Pan,Jin Wang,Tongyu Bao,Xinjuan Liu,Zhihong Tang,Huixin Xiu,Jing Li
The lateral size of graphene nanosheets plays a critical role in the properties and microstructure of 3D graphene as well as their application as supports of electrocatalysts for CO2reduction reactions (CRRs). Here, graphene oxide (GO) nanosheets with different lateral sizes (1.5, 5, and 14 µm) were utilized as building blocks for 3D graphene aerogel (GA) to research the size effects of GO on the CRR performances of 3D Au/GA catalysts. It was found that GO-L (14 µm) led to the formation of GA with large pores and a low surface area and that GO-S (1.5 µm) induced the formation of GA with a thicker wall and isolated pores, which were not conducive to the mass transfer of CO2or its interaction with catalysts. Au/GA constructed with a suitable-sized GO (5 µm) exhibited a hierarchical porous network and the highest surface area and conductivity. As a result, Au/GA-M exhibited the highest Faradaic efficiency (FE) of CO (FECO= 81%) and CO/H2ratio at −0.82 V (vs. a Reversible Hydrogen Electrode (RHE)). This study indicates that for 3D GA-supported catalysts, there is a balance between the improvement of conductivity, the adsorption capacity of CO2, and the inhibition of the hydrogen evolution reaction (HER) during the CRR, which is related to the lateral size of GO.
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高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2023
·Vol. 58
·期 44
·16891-16904
·
IF 4.5
Wu Fanghui,Xu Xudong,Luo Xiangrui,Cheng Yuansheng,Xu Hong,Yuan Guozan,Kang Yanshang,Wei Xianwen,Wang Wenhai,Yan Zhengquan
To alleviate the global warming, it is necessary to transform carbon dioxide (CO 2 ) into carbon monoxide (CO) through an expedient and resultful approach. In this work, a novel kind of Schiff base-cobalt ion complexes (CHE-Co) was constructed with 5-chorosalicylaldehyde, acetylglycine, acetic anhydride and CoCl 3 ·6H 2 O as raw materials. It was discovered that CHE-Co exhibits outstanding photocatalytic activity to reduce CO 2 to CO (selectivity: 91%) in an H 2 O/CH 3 CN solution ( V:V = 1:4) under the irradiation of a LED-simulated solar lamp ( λ > 400 nm, 90 mW cm –2 ). Under the optimized conditions, the yield of CO photo-catalytically reduced from CO 2 can reach 15.92 μmol, with TON value of 1592 and TOF value of 159.2 h −1 . The photo-catalytic mechanism of CHE-Co was proposed that CHE-Co with a positive E onset can drive electrons shift from excited-state photosensitizer [Ru(phen) 3 ] 2+* to CHE-Co via a single-molecule rate control reaction.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Pengchao Zang,Jiyun Tang,Hao Zhang,Xiaozhe Wang,Peiyu Zhao,Lin Cui,Juan Chen,Pei Zhao,Yong Dong
The solid amine adsorbents are potential candidates as materials for post-combustion capture technologies. The type of organic amine and porous material are the key factors influencing the amine-based solid adsorbent performance. Furthermore, there has been relatively little research on the matching mechanism between organic amines and porous materials. This study aims to investigate the effect of the degree of matching between different organic amines and porous materials (X-5 resin) on the performance of CO 2 capture. The results indicated that 30 wt% TETA was the highest matching degree with X-5 and had the maximum CO 2 adsorption of 205.48 mg/g at 30 ℃. The matching degree between the four amines and the X-5 resin followed TETA > TEPA > PEHA > PEI. Since TETA has the simplest molecular structure, it can be conveniently dispersed in the X-5 pores, which not only significantly improves the utilization of active sites but also prevents the phenomena of agglomeration or sintering. Meanwhile, X-5-30TETA has the highest adsorption energy E ads (−85.22 kJ/mol) and the smallest spatial potential resistance, decreasing the mass transfer resistance effectively, thus further increasing the adsorption capacity. Furthermore, the adsorption kinetics results showed that the Avrami model can relatively accurately predict the experimental results of X-5-TPHI CO 2 adsorption. Finally, the in situ DRIFTS indicated that the CO 2 adsorption reaction over X-5-30TETA followed predominantly an amphipathic centipede mechanism. This work provides a new idea for the investigation of the matching mechanism between organic amines and porous materials.
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Yiting Xu,Xiaobo Yu,Meiling Chen,Yi Sun,Wei Zhang,Yajin Fang,Lanyun Fang,Haining Na,Fei Liu,Jin Zhu
Fabrication of multi-responsive fluorescent sensors for real-time and visual monitoring or detection is practical and challenging. Herein, a novel cellulose-based fluorescent functional material with dual-responsive properties arising from two different functional sites was successfully designed and prepared in a CO 2 switchable solvent. Cellulose was effectively dissolved in this solvent and easily functionalized by successively grafting poly (lactic acid) and 7-hydroxy-4-trifluoromethyl coumarin (HFC) onto the cellulose backbone, resulting in C- g -PLLA/HFC with good processibility and fluorescence quenching response (turn off) towards Fe 3+ due to the coordination of Fe 3+ with the carbonate linkage. Acetylation of HFC under microwave-assisted conditions gave rise to C- g -PLLA/HFC-Ac which showed fluorescence enhancement response (turn on) to various organic amines because of the removal of the acetyl group by aminolysis reaction. Therefore, they could be respectively used for selective identification and detection of Fe 3+ , and real-time, accurate and visual monitoring of aquatic product freshness. Furthermore, an interesting application for irreversible information encryption was demonstrated by combining the dual-responsive property. This study suggests a new strategy for constructing cellulose-based functional material with multiple responsiveness and applications.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2023
·
IF 4.2
Xinbao Zhang,Guanghui Zhang,Xiangkun Zhou,Zhiqun Wang,Yi Liu,Jie Zhu,Chunshan Song,Xinwen Guo
Interest in identifying the structure of the catalysts in the reaction atmosphere has grown, but it remains challenging, especially when the changes only occur on the surface. Herein, we track the reaction-induced structural changes of ZnO/ZrO2 and their consequent effects on the activity and selectivity of CO2 hydrogenation. Utilizing a combination of in situ infrared and controlled experiments, we meticulously investigate the dynamic changes of the catalyst’s surface structure with time on stream. The reaction-driven growth of ZnOx clusters is correlated with the enhanced CO2 hydrogenation activity of ZnO/ZrO2. Furthermore, in situ infrared results show that the aggregation of ZnOx clusters promotes hydrogen activation, thereby facilitating the synthesis of methanol. The modification of the interfacial sites confirms the significance of the ZnO–ZrO2 interface as the main site for CO formation, while the surface of ZnOx clusters predominantly contributes to methanol synthesis at low zinc loading. These findings advance our comprehension of the structure–activity relationship of zinc-based catalysts for CO2 hydrogenation.
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