ACS Catalysis
·
2025
·
IF 13.1
Qiyou Wang,Yusen Xiao,Feng Li,Yao Tan,Yuxiang Liu,Franz Gröbmeyer,Kang Liu,Junwei Fu,Hongmei Li,Cheng-Wei Kao,Ting-Shan Chan,Rui-kai Miao,Liyuan Chai,Emiliano Cortés,Min Liu
In acidic CO2 electroreduction reaction (CO2RR), excessive H* adsorption from high proton concentrations suppresses *CO coverage on Cu-based catalysts, limiting multicarbon (C2+) product formation. Here, we introduce a K+ insertion strategy via an interlayer electric field (IEF) between the layers of Cu nanosheets (K+-Cu NS) to strengthen *CO adsorption and boost C2+ selectivity. Finite element method (FEM) simulations verified the role of the IEF in enriching K+ ions, meanwhile density functional theory (DFT) calculations demonstrated these enriched K+ ions facilitate stronger *CO adsorption. Ar+ ion-etching-assisted X-ray photoelectron spectroscopy (XPS) and operando Raman spectroscopy confirmed the structured K+ stuffing. Operando attenuated total reflection infrared spectroscopy (ATR-IR) demonstrated the enhanced *CO adsorption on K+-Cu NS. As a result, the K+-Cu NS catalyst achieved an ultrahigh cathodic energy efficiency of 42.5% and a remarkable Faradaic efficiency of 80.3% for C2+ products in a flow cell. This work highlights a novel cation regulation strategy for advancing the acidic CO2RR efficiency.
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NEW JOURNAL OF CHEMISTRY
·
2025
·
IF 2.5
Xiaoyuan Luo,Zhenze Han,Xuetian Guo,Yu Wei,Yan Gao
Bismuth-based metal–organic frameworks (MOFs) have shown promise in the electrocatalytic CO2 reduction reaction (ECO2RR) due to their abundant active sites and high selectivity. In this study, microfluidic synthesis technology was innovatively introduced to achieve the continuous synthesis of the bismuth-based MOF material CAU-17. Compared with the hydrothermal method, by adjusting the flow rate while keeping the temperature and Bi3+ reaction concentration constant, the particle size and morphology could be effectively controlled, and the synthesis time was reduced to 1/36 of that of the traditional method. CAU-17 particles with different sizes showed different reactivity sensitivities to the ECO2RR. CAU-17-F60 with the smallest particle size showed the highest Faraday efficiency of 92.79% for formate at −1.2 VRHE, along with a larger electrochemically active surface area and lower interfacial resistance. It could be electrolyzed stably for 12 h, during which the average FEformate remained above 90% all the time. This study thoroughly demonstrates the significant potential of microfluidic technology in the precise control of fine structures and performance optimization of MOF catalysts, offering a new idea and a generalizable path for the sustainable preparation of efficient ECO2RR catalysts.
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Nature Nanotechnology
·
2025
·
IF 34.9
Song Yun,Musgrave Charles B.,Su Jianjun,Huang Libei,Guo Weihua,Liu Yong,Li Geng,Xin Yinger,Zhang Qiang,Feng Xing,Liao Can,Liu Shunjie,Kwok Ryan Tsz Kin,Lam Jacky W. Y.,He Mingming,Choong Kai Shen,Feng Zhenxing,Tang Ben Zhong,Goddard William A.,Ye Ruquan
Electrosynthesis of value-added chemicals in strong acids can mitigate carbon loss and the operational cost of CO 2 reduction reaction (CO 2 RR). However, molecular catalysis for CO 2 RR is typically conducted in neutral or alkaline environments. CO 2 RR in acidic media is challenged by the scarcity of catalyst candidates, competitive hydrogen evolution and slow product formation. Here we report a locally ionic yet simultaneously hydrophobic and aerophilic layered structure that modulates the microenvironment surrounding cobalt phthalocyanine (CoPc) molecular catalysts, enabling efficient, multielectron CO 2 RR in acidic media. Experiment and theoretical modelling reveal that the polarized electrostatic field arising from the cationic groups suppresses hydronium migration. Concurrently, the van der Waals forces between the reactant gas and alkyl groups improve local CO availability, combining to achieve a methanol partial current density of 132 mA cm −2 with 62% selectivity at a pH of ~1 and –1.37 V RHE for CoPc, exceeding previous reports on neutral or alkaline electrolytes. The improved CO coverage also enables the detection of *CHO and *CO intermediates from in situ spectroscopy. We validate our strategy on various molecules, which champion the efficient inhibition of hydrogen evolution and improved CO 2 RR partial current density in acidic media. CoPc-based layered structure with similar ionic, hydrophobic and aerophilic interfaces also yields comparable methanol productivity.
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PubMed
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Teng Xu,Guilin Yin,Fengyu Wang,Fan Yang,Junli Xu,Jinyu Ye,Danfeng Wu,Xiaoxu Duan,Weng Fai Ip,Sen Lin,Haifeng Xiong
Integrated CO2 capture and electrochemical utilization (ICCU) is promising for decarbonization by bypassing energy-intensive desorption/compression steps compared to conventional CO2 capture and utilization (CCU) systems. However, the critical barrier in ICCU is the mass transfer limitations of carbon-containing species from amine solutions to electrode surfaces, leading to a low CO2 conversion and a high hydrogen evolution reaction (HER). To address this issue, we introduce an interfacial engineering strategy to create a microenvironment using quaternary ammonium cationic surfactants for enhanced CO2 conversion. In the cetyltrimethylammonium bromide (CTAB)-modified monoethanolamine (MEA) system, a Ag nanoparticle achieved 63.4% CO Faradaic efficiency at −0.82 V vs RHE, representing a 4.7-fold improvement over unmodified system. Chain-length optimization revealed that short-chain surfactants lacked sufficient hydrophobicity, while long-chain variants increased the mass transfer resistance, positioning CTAB (C16) as the optimal candidate. The strategy demonstrates amine versatility and 50 h of recyclability without catalyst/amine degradation. In situ spectra and density functional theory calculation elucidated that CTAB has dual roles, i.e., CTAB cation (CTA+) adsorption repels the aggregation of protonated amine (MEAH+) on the electrode surface and the hydrophobic alkyl chains enrich the carbon-containing species. This work provides a mechanistic framework for designing efficient and stable ICCU systems through creating a microenvironment.
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Science Advances
·
2023
·Vol. 9
·期 24
·
IF 13.6
Mingrui Wang,Peng Wang,Guanghui Zhang,Zening Cheng,Mengmeng Zhang,Yulong Liu,Rongtan Li,Jie Zhu,Jianyang Wang,Kai Bian,Yi Liu,Fanshu Ding,Thomas P. Senftle,Xiaowa Nie,Qiang Fu,Chunshan Song,Xinwen Guo
The decomposition of cobalt carbide (Co 2 C) to metallic cobalt in CO 2 hydrogenation results in a notable drop in the selectivity of valued C 2+ products, and the stabilization of Co 2 C remains a grand challenge. Here, we report an in situ synthesized K-Co 2 C catalyst, and the selectivity of C 2+ hydrocarbons in CO 2 hydrogenation achieves 67.3% at 300°C, 3.0 MPa. Experimental and theoretical results elucidate that CoO transforms to Co 2 C in the reaction, while the stabilization of Co 2 C is dependent on the reaction atmosphere and the K promoter. During the carburization, the K promoter and H 2 O jointly assist in the formation of surface C * species via the carboxylate intermediate, while the adsorption of C * on CoO is enhanced by the K promoter. The lifetime of the K-Co 2 C is further prolonged from 35 hours to over 200 hours by co-feeding H 2 O. This work provides a fundamental understanding toward the role of H 2 O in Co 2 C chemistry, as well as the potential of extending its application in other reactions.
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Journal of Energy Chemistry
·
2018
·
IF 3.886
Yunfeng Bao,Chunlei Huang,Limin Chen,Yu dong Zhang,Long Liang,Jinjun Wen,Mingli Fu,Junliang Wu,Daiqi Ye
Anatase TiO 2 nanosheets (-ns-) with dominant exposed {001} facets were used as support to load copper, and the synthesized Cu/TiO 2 -ns catalysts were evaluated for CO 2 hydrogenation to methanol. Under the reaction conditions, P = 3.0 MPa, T = 260 °C, V (N 2 ): V (H 2 ): V (CO 2 ) = 8:69:23 and gas hourly space velocity (GHSV) = 3600 mL g −1 h −1 , the methanol yield reached an appealing high value, 5.6%. Copper-loading amount, calcination temperature and reduction atmosphere have been investigated in this work, which significantly influence the particle sizes of copper and/or the defect concentration in TiO 2 , then leading to different catalytic performance. Characterizations of XRD, EPR, CO 2 -TPD and FTIR demonstrate that higher specific surface area of Cu is good for the hydrogenation of CO 2 and adequate amount of Ti 3+ plays important roles in CO 2 activation. Both of them facilitate high turnover frequency (TOF) of methanol formation.
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KEY ENGINEERING MATERIALS
·
2015
·
IF 0
Peng Peng Lv,Feng Wang,Yu Hai Guo,Hong Yan Tang
In this study, hydrophilic PTFE hollow fiber membranes were prepared and applied for CO2 desorption via a membrane flash process, which is a new CO2 desorption process by utilizing waste thermal energy. The methyldiethanolamine was selected as the absorbent. Effects of the flashing temperature, flashing pressure, rich solution flow rate and MDEA concentration on CO2 release ratio and CO2 desorption flux were deeply investigated. The results show that flashing temperature is positive to the CO2 release ratio and CO2 desorption flux. However, the flashing pressure, rich solution flow rate and MDEA concentration are negative to the CO2 release ratio and CO2 desorption flux.
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DOI
Science China-Materials
·
2024
·Vol. 67
·期 3
·788-795
·
IF 6.8
Song Dewen,Zhang Shipeng,Ning Hui,Fei Xiang,Wang Mingwang,Wang Xiaoshan,Wu Wenting,Zhao Qingshan,Li Yongzhe,Wu Mingbo
CO 2 electroreduction is an alluring technology for high-value CO 2 utilization and intermittent electrical energy storage. Self-supporting catalysts with high efficiency have clear advantages over powder ones in electrode construction but still lack effective synthesis methods. In this work, a self-supporting BiCu/carbon hybrid nanofiber membrane (BiCu/CHNM) was synthesized by electrospinning-calcination and employed directly as a working electrode in a flow cell for CO 2 electroreduction to formate with a high Faradaic efficiency of 87.67% at a partial current density of 142.9 mA cm −2 . In stability tests, the Faradaic efficiency of formate remained at 80% for 50 h at high partial current densities (>100 mA cm −2 ). In-situ Raman spectra and density functional theory calculations confirmed that copper doping lowers the energy barrier of HCOO − formation on the Bi (012) plane and increases the conductivity of the carbon nanofiber network. Due to the well-designed conductive framework and the highly dispersed BiCu active sites, this hybrid membrane shows high activity, high selectivity, and long stability simultaneously.
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ENERGY & FUELS
·
2019
·
IF 3.021
Ke Wang,Feng Gu,Peter T. Clough,Pengfei Zhao,Edward J. Anthony
Calcium looping (CaL) technology is potentially one of the more attractive ways to capture CO2 from fossil fuel power plants. However, with increasing numbers of reaction cycles, the CO2 capture capacity rapidly decreases. To address this shortcoming, limestone-dolomite mixtures reacted with gluconic acid to form Ca-Mg gluconics were explored to prepare highly effective, MgO-stabilized, CaO sorbents that exhibited a high and stable CO2 capture capacity over multiple cycles. The sorbents were all tested over 10 carbonation-calcination cycles, under realistic CaL conditions (calcination in a high CO2 concentration). The results indicate the development of an effective homogeneous composition between CaO and MgO, due to the small CaO crystallite size, porous texture, and nanosheet (∼100 nm thick) morphology. This provides sufficient void space for the volume expansion during carbonation to mitigate the effects of repeated cycle sintering and retain structural stability. Here, MgO content as low as 10 mol % was able to ensure a superior CO2 capture performance with a fast carbonation rate, high CO2 carrying capacities, and remarkable stability. Furthermore, these sorbents retained a conversion (above 90%) over multiple cycles following a recarbonation step.
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高影响因子
Materials
·
2026
·Vol. 19
·期 21
·4500
·
IF 3.7
Shanshan Lin,Guangjing Feng,Xiaoyan Sun
Strong retention of coordinated CO can divert molecular CO2reduction from product release toward persistent carbon-containing species and catalyst deactivation. We examine this competition in a Cu(II)-derived Cudpk system using electrochemistry–electrospray ionization mass spectrometry (EC-ESI-MS), collision-induced dissociation (CID) and AI-assisted pathway simulation. Time-resolved EC-ESI-MS during the potential-pulse sequence detected Cudpk ions assigned to -–CO, –COH, –CHOH and –CH-associated compositions. In separate post-electrolysis solution samples, anm/z= 260 CH-associated ion was detected after constant-potential operation but was not obvious after approximately 16 h of pulsed operation. Double-ended surface walking (DESW) searches on LASPAI use a generalized global neural network (GGNN) potential to evaluate energies and forces. The resulting profile places a high energetic cost on CO release and identifies a competing route from retained CO toward a Cu-bound carbon state. Pulsed operation resolves this contradiction: periodic potential pulses suppress the accumulation of residual carbon-containing species, thereby maintaining the turnover of the CO formation reaction. The AI-derived energy profile and pulse-dependent mass spectrometry data support a proposed deactivation pathway involving further conversion of strongly retained CO into persistent carbon-associated species. The reduced persistence of CH-associated ions after pulsed operation, together with sustained CO production, is consistent with mitigation of this pathway.
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Greenhouse Gases-Science and Technology
·
2015
·Vol. 5
·期 5
·682-694
·
IF 2.147
Tao Wang,Wei Yu,Mengxiang Fang,Hui He,Qunyang Xiang,Qinhui Ma,Menglin Xia,Zhongyang Luo,Kefa Cen
Nanoparticles suspended in solutions are considered to have the potential to enhance gas-liquid mass transfer and have been studied for gas separation. In order to reveal the mechanisms of kinetics enhancement, the diffusion and reaction process should be carefully examined. In this paper, CO 2 absorption kinetics of amine-based solutions with additive of SiO 2 and Al 2 O 3 nanoparticles were investigated by wetted-wall column experiments. Measurements at different conditions, including solid loading, pressure, and solvent flow rate, show a significant enhancement on CO 2 absorption kinetics. The experiment and model analysis indicate that the micro convective motion induced by particle Brownian movement plays a primary role in mass transfer enhancement. Three solutions, MEA, MDEA, and PZ which have different kinetics were selected to study the impact of nanoparticles on absorption kinetics of solutions with different reaction rate. It is interesting to find that the increased ratio of absorption kinetics by nanoparticle follows the same order with increased solvent reaction rate with CO 2 , which is PZ > MEA > MDEA. The wetted-wall kinetic model indicates that a diffusion controlled kinetics for PZ solution could result in much more significant kinetic enhancement with additives of nanoparticles. By operation conditions optimization, the liquid side mass transfer rate of MEA solution can be increased over 15%.© 2015 Society of Chemical Industry and John Wiley & Sons, Ltd
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高影响因子
STARCH-STARKE
·
2019
·
IF 1.795
Si-yu Mi,Liang-shuang Sun,James Runt,Mu-chen Kuo,Kuo-shien Huang,Jen-taut Yeh
This paper describes sodium hexametaphosphate (SHMP)-modified thermoplastic starch (TPS) resins (scCO 2 TPS 100 SHMP x ) gelatinized and/or modified with the aid of supercritical carbon dioxide (scCO 2 ). TPS and scCO 2 TPS 100 SHMP x exhibit considerably higher melt flow rates, moisture resistance, and initial and retention tensile strength values than TPS and TPS 100 SHMP x prepared using conventional atmospheric pressure. Only V h -type crystals are found in conditioned scCO 2 TPS 100 SHMP x , which show significantly lower melting temperatures (≈19 °C) than the corresponding conditioned TPS 100 SHMP x . Relative to TPS 100 SHMP x , conditioned scCO 2 TPS 100 SHMP x show a weaker hydrogen bonding network among the hydroxyl groups in the amylopectin chains and considerably less retrogradation. The loosely hydrogen-bonded hydroxyl groups found in conditioned scCO 2 TPS 100 SHMP x can be replaced with stronger hydrogen bonds involving the phosphate groups of SHMP through the proper modification of scCO 2 TPS 100 SHMP x .
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高影响因子
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