ENERGY & FUELS
·
2026
·Vol. 40
·期 35
·19588-19599
·
IF 6
Li Zhefeng,Cheng Jun,Sun Yunshuyu,Qiu Yi,Lin Zhen,Mao Yuxiang,Xia Rongxin,Zhang Meng
Cu-based
catalysts are promising for CO 2 -to-methanol
conversion, but their activity and stability are usually compromised
by the accumulation of byproduct water. Although physically mixing
hydrophobic additives with Cu-based catalysts can facilitate water
removal, how to regulate the water-removal kinetics in this process,
as well as its impact on the reaction kinetics of CO 2 hydrogenation
to methanol, remains insufficiently understood. Herein, by modifying
the polydivinylbenzene (PDVB) with porosity, we regulate the surface
hydrophobicity of its mixture with a layered double hydroxide (LDH)-derived
CuZnAlMg catalyst, thereby enhancing the water removal kinetics on
the mixed catalyst surface. In contrast to nonporous PDVB, porous
PDVB, with a substantially higher surface area and abundant mesopores,
effectively creates additional H 2 O transfer channels. This
facilitates rapid water removal, which in turn inhibits the oxidation
of Cu nanoparticles and ensures the re-exposure of oxygen-vacancy
active sites for sustained catalysis. Furthermore, water removal also
accelerates the formation and subsequent hydrogenation of intermediates
for higher activity. Consequently, a high space-time yield of methanol
of 519.89 g MeOH kg cat –1 h –1 and a CO 2 conversion rate of 26.35% are
achieved at 5 MPa and 260 ° C. The mixed catalyst exhibits
excellent stability over 200 h of continuous operation. This work
offers a simple yet robust strategy for regulating catalyst hydrophobicity
toward efficient CO 2 hydrogenation to methanol.
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ACS Applied Energy Materials
·
2026
·
IF 5.5
Wu Pengxuan,Ding Yusong,Li Bingshuang,He Yunxia,Liu Qian,Huang Xiaoxi
This study reports a mesoporous carbon confinement strategy for enhancing the mass activity and structural durability of Au-based catalysts toward electrochemical CO 2 reduction reaction (CO 2 RR) to CO. Glutathione-protected Au clusters were introduced into polyaniline-derived mesoporous carbon (PDMC), followed by thermal ligand removal, producing ultrasmall Au nanoparticles uniformly embedded within a conductive N-doped carbon framework. The mesoporous carbon matrix effectively restricts Au growth and suppresses nanoparticle aggregation, thereby preserving abundant low-coordinated Au surface sites while maintaining accessible channels for charge and mass transport. The optimized Au@PDMC-30 catalyst delivers a CO Faradaic efficiency of 90.0 ± 1.3% at –0.9 V vs reversible hydrogen electrode in an H-type cell and maintains stable CO production for over 24 h without obvious Au aggregation. More importantly, under flow-cell conditions, Au@PDMC-30 achieves a high CO mass activity of 1192.4 mA mg –1 , approximately twice that of commercial Au/C, demonstrating greatly improved precious-metal utilization. In situ Fourier transform infrared spectroscopy and density functional theory calculations reveal that the confined low-coordinated Au sites possess an optimized electronic structure that facilitates *COOH formation, thereby accelerating the CO 2 to CO pathway. This work highlights confinement engineering of ultrasmall noble-metal nanoparticles as an effective route to improve catalytic selectivity, durability, and mass-normalized activity for CO 2 RR.
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Zhibing Wen,Rong Zhang,Yong Zhu,Hua Gao,Ran Zhao,Zhi Chen,Siyao Wang,Shuanglin He,Ya-Qiong Zhang,Rong-Zhen Liao,Fei Li
Electrocatalytic and photoelectrochemical reduction of carbon dioxide (CO 2 ) to hydrocarbons remains a significant challenge, particularly for molecular catalysts that typically yield two-electron products like CO and HCOOH. Here, high selectivity toward CH 4 is achieved using a [Cu II (phen) 2 (NO 3 )] + (phen = 1,10-phenanthroline) molecular catalyst immobilized on multi-walled carbon nanotubes (CNTs) in aqueous solution. At −1.42 V versus the reversible hydrogen electrode (RHE), the electrode drives partial current densities of −10.8 mA cm −2 for CH 4 production from CO 2 electroreduction, corresponding to a Faradaic efficiency of 50 %. This value is among the highest reported for molecular catalysts. Conventional characterization and in situ measurements are conducted to verify the molecular identity of [Cu II (phen) 2 (NO 3 )] + , with no observed formation of Cu nanoparticles. Mechanistic studies reveal the [Cu I (phen)(H 2 O)] + species as the active intermediate for CO 2 activation. Furthermore, an assembly of the [Cu II (phen) 2 (NO 3 )] + and CNTs on a Si|TiO 2 substrate is used to construct a molecular photocathode (Si|TiO 2 |CNT-[Cu II (phen) 2 (NO 3 )] + | [Cu II (phen) 2 (NO 3 )] + ) for photoelectrochemical CO 2 reduction. The hybrid photocathode produces a photocurrent density of −5.7 mA cm −2 , achieving Faradaic efficiencies of 10 % and 5 % for CH 4 and C 2 H 4 production at −0.7 V vs. RHE, respectively. This represents the first example of photoelectrochemical CO 2 -to-hydrocarbons conversion employing a photocathode based on a low-cost molecular catalyst.
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Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Naveed Ahmad,Shumaila Mustafa,Cui Ping
Biomass-derived carbons are promising supports for electrochemical CO 2 reduction (ECO 2 R) due to their natural abundance and renewability. However, achieving high selectivity and industrially relevant current densities with biomass-derived carbon catalysts remains challenging. Here, inspired by the porous microchannel and bristle-like structure of Setaria viridis (SV), a one-pot co-pyrolysis strategy was employed to synthesize hierarchically porous silver-decorated nitrogen-doped carbon catalysts. The SV-derived carbon, combined with optimized nitrogen doping and silver decoration (Ag/N-SV1), yields a hierarchically porous carbon catalyst with tuned electronic states that enhance CO 2 adsorption and stabilize the ⁎ COOH intermediate, thereby improving CO selectivity. In an H-cell, Ag/N-SV1 achieved a CO Faradaic efficiency (FE CO ) of 89% with a partial current density (j CO ) of -6.7 mA cm -2 at -0.98 V vs. RHE, while maintaining stable operation for 20 hours. In contrast, nitrogen-doped SV (N-SV1) primarily produced formate, highlighting the critical role of Ag in CO selectivity. Furthermore, the hydrophobically treated Ag/N-SV1 gas diffusion electrode (GDE) achieved a j CO of -123 mA cm -2 in the flow cell, demonstrating scalability and practical promise. Density functional theory (DFT) calculations revealed that Ag-N coordination lowers the energy barrier for ⁎ COOH formation, resulting in enhanced CO selectivity. This study highlights Setaria viridis as a renewable and sustainable biomass precursor, validating the co-pyrolysis approach as an effective strategy for designing cost-effective Ag-N materials for sustainable electrochemical applications.
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JOURNAL OF MEMBRANE SCIENCE
·
2022
·
IF 10.53
Shuo Li,Shu-Mei Chang,Ming-Jie Yin,Wen-Hai Zhang,Wei-Shi Sun,Angus Shiue,Quan-Fu An
Poly (ethylene oxide) (PEO) membranes are attractive for CO 2 capture due to the particular dipolar–quadrupolar interaction between EO units and CO 2 molecules, which offer high CO 2 /N 2 selectivity. However, the low CO 2 permeability of PEO membranes hampers their practical applications. Herein, a simple solvothermal annealing approach was proposed to enhance the flexibility of PEO chains via ‘activating’ the disengagement and rearrangement of side chains, which is essential for boosting the gas permeability . The effects of solvothermal annealing temperature, time, and solvent on the CO 2 /N 2 separation performance were comprehensively investigated. The mechanism for the performance enhancement was proposed: a “highway” for gas transportation was built up by the released flexible side chains, which were confirmed by the mechanical and Li ion conductivity characterizations. The optimized PEO membrane offers a superior CO 2 permeability of 1294 Barrer, a high CO 2 /N 2 selectivity of 50, and 110-h long-term running stability, being beyond the 2008 Robeson’s upper bound line and promoting the practical application of PEO membranes in CO 2 capture by reducing the cost.
研究领域:
高分子科学
·
膜分离技术
·
气体分离
·
环境工程
·
材料化学
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AICHE JOURNAL
·
2026
·
IF 4.4
Chaodi Jin,Heli Tian,Ruoyu Hu,Beiqi Sun,Xing Hu,Min Xiao,Hongxia Gao,Teerawat Sema,Zhiwu Liang
Liquid–liquid phase separation is an interesting phenomenon that generates two immiscible liquid phases during CO 2 absorption or temperature swing. It provides a promising opportunity to optimize CO 2 capture processes and reduce the energy penalty for solvent regeneration. However, precise control of phase behavior remains challenging. This work achieves controllable phase separation in amine-ether-water systems. Results show that adjusting the ether-to-water mass ratio enables the correlation between critical CO 2 loading and temperature to reversibly shift from negative to positive. This rule is verified in various amines and ethers. Synergistic effects of temperature and CO 2 absorption on phase separation are revealed by 13 C NMR and molecular dynamics simulations. This study deepens the understanding of phase separation and offers a theoretical basis for developing high-performance CO 2 absorbents for industrial applications.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2026
·
IF 9.6
Di Gao,Jian-Zhi Yang,Heng-Yu Wei,Kong-Zhai Li,Min Lin,Xing Zhu
C e-e Zr solid solution formation strengthens the metal-support interaction. • The catalyst reached 79.02% CO 2 conversion and methanation rate 26.35 mmol·g cat −1 ·h −1 . • Dual-role oxygen vacancies enhance charge separation and CO 2 activation. Photothermal Carbon dioxide (CO 2 ) hydrogenation is a promising strategy for solar-fuel production, but its performance is often limited by inefficient charge separation and poor low-temperature activity. Herein, Ni/Ce-Zr solid solution catalysts were developed by introducing lattice distortion to regulate the electronic structure and generate abundant oxygen vacancies. The resulting oxygen vacancies promote charge separation, enhance CO 2 activation, and strengthen the photothermal synergistic effect. Among the catalysts, 20Ni/Ce 0.75 Zr 0.25 O 2 exhibited the best performance, achieving 79.02% CO 2 conversion, over 99.00% CH 4 selectivity, a methanation rate of 26.35 ± 0.05 mmol·g cat −1 ·h −1 , and an apparent activation energy of 16.23 ± 0.70 kJ/mol at 250 °C, while maintaining stable operation for over 180 h. In situ DRIFTS results reveal that abundant oxygen vacancies facilitate the hydrogenation of key intermediates and suppress carbonate accumulation, thereby preventing catalyst deactivation. These findings demonstrate that oxygen-vacancy engineering is an effective approach for improving photothermal CO 2 methanation and provide guidance for the design of efficient solar-driven CO 2 conversion catalysts. Oxygen Vacancy-Mediated Photothermal CO 2 Methanation over Ni/Ce-Zr Solid Solution. Download: Download high-res image (208KB) Download: Download full-size image
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PubMed
高影响因子
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
·
2026
·
IF 4.4
Mengyuan Zhao,Lulu Ren,Yameng Li,Xin Lu,Jingwen Meng,Xiaodi Liu,Xin Li,Fengyun Su,Zhonghua Fu,Xiaoli Jin,Haiquan Xie
A Synergistic strategy that integrates the intrinsic polarization field with heterojunction interfacial engineering is demonstrated for boosting photocatalytic CO 2 reduction. In the engineered Bi 4 O 5 Br 2 /Nb 2 O 5 heterojunction, a structure has not been previously reported for CO 2 photoreduction to date, the intrinsic polarization field of Bi 4 O 5 Br 2 facilitates initial charge separation within the bulk phase. The type-ii interfacial field drives the transfer of separated electrons toNb 2 O 5 , achieving effective spatial separation of carriers. This efficient charge separation promotes surface reactions, as evidenced by in situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS), which reveals accelerated formation and transformation of key intermediates (*CO 2 , *COOH and *CHO) along the reaction pathways toward CO and CH 4 . Using ultrapure water as the proton source, the CO and CH 4 production rates of the optimal composite reach 4.6 and 3.7 μmol g −1 h −1 , respectively, which are 2.0 and 4.6 times higher than those of pristine Bi 4 O 5 Br 2 . In contrast to conventional heterojunction strategies that focus solely on interfacial band engineering, this work simultaneously leverages the intrinsic properties of bulk materials, offering a new design paradigm for efficient CO 2 photoreduction.
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高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-13
·
IF 16.6
Sun Ji Wei,Wu Xuefeng,Liu Peng Fei,Chen Jiacheng,Liu Yuanwei,Lou Zhen Xin,Zhao Jia Yue,Yuan Hai Yang,Chen Aiping,Wang Xue Lu,Zhu Minghui,Dai Sheng,Yang Hua Gui
Practical electrochemical CO 2 -to-CO conversion requires a non-precious catalyst to react at high selectivity and high rate. Atomically dispersed, coordinatively unsaturated metal-nitrogen sites have shown great performance in CO 2 electroreduction; however, their controllable and large-scale fabrication still remains a challenge. Herein, we report a general method to fabricate coordinatively unsaturated metal-nitrogen sites doped within carbon nanotubes, among which cobalt single-atom catalysts can mediate efficient CO 2 -to-CO formation in a membrane flow configuration, achieving a current density of 200 mA cm −2 with CO selectivity of 95.4% and high full-cell energy efficiency of 54.1%, outperforming most of CO 2 -to-CO conversion electrolyzers. By expanding the cell area to 100 cm 2 , this catalyst sustains a high-current electrolysis at 10 A with 86.8% CO selectivity and the single-pass conversion can reach 40.4% at a high CO 2 flow rate of 150 sccm. This fabrication method can be scaled up with negligible decay in CO 2 -to-CO activity. In situ spectroscopy and theoretical results reveal the crucial role of coordinatively unsaturated metal-nitrogen sites, which facilitate CO 2 adsorption and key *COOH intermediate formation.
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ACS Nano
·
2023
·
IF 17.1
Pengyu Song,Botao Hu,Di Zhao,Jiantao Fu,Xiaoran Su,Wuyi Feng,Ke Yu,Shoujie Liu,Jiatao Zhang,Chen Chen
Cu single-atom catalysts (Cu SACs) have been considered as promising catalysts for efficient electrocatalytic CO2 reduction reactions (ECRRs). However, the reports on Cu SACs with an asymmetric atomic interface to obtain CO are few. Herein, we rationally designed two Cu SACs with different asymmetric atomic interfaces to explore their catalytic performance. The catalyst of CuN3O/C delivers high ECRR selectivity with an FECO value of above 90% in a wide potential window from −0.5 to −0.9 V vs RHE (in particular, 96% at −0.8 V), while CuCO3/C delivers poor selectivity for CO production with a maximum FECO value of only 20.0% at −0.5 V vs RHE. Besides, CuN3O/C exhibited a large turnover frequency (TOF) up to 2782.6 h–1 at −0.9 V vs RHE, which is much better than the maximum 4.8 h–1 of CuCO3/C. Density functional theory (DFT) results demonstrate that the CuN3O site needs a lower Gibbs free energy than CuCO3 in the rate-determining step of CO desorption, leading to the outstanding performance of CuN3O/C on the process of ECRR-to-CO. This work provides an efficient strategy to improve the selectivity and activity of the ECRR via regulating asymmetric atomic interfaces of SACs by adjusting the coordination atoms.
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高影响因子
Nano Research
·
2023
·Vol. 16
·期 7
·8757-8764
·
IF 9.9
Liang Zhong,Song Lianpeng,Sun Mingzi,Huang Bolong,Du Yaping
Currently, single-atom combo catalysts (SACCs) for carbon dioxide reduction reaction (CO 2 RR) to the formation of HCOOH are still very limited, especially the lanthanide-based SACCs. In this work, the novel SACCs with atomically dispersed In and Ce active sites were successfully prepared on the nitrogen-doped carbon matrix (InCe/CN). Both aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) images and the extended X-ray absorption fine structure (EXAFS) spectra proved the well-isolated In and Ce atoms. The as-prepared InCe/CN shows a high Faradaic efficiency (FE) (77%) and current density of HCOOH formation ( j HCOOH ) at −1.35 V vs. reversible hydrogen electrode (RHE), much higher than the single atom catalysts. Theoretical calculations have indicated that the introduced Ce single atom sites not only significantly promote electron transfer but also optimize the In-5p orbitals towards higher selectivity towards the HCOOH formation. This work innovatively extends the design of SACCs towards the main group and Ln metals for more applications.
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Journal of Environmental Chemical Engineering
·
2023
·
IF 7.7
Xingqian Wang,Yifei Wang,Yongjiang Shan,Xuerong Wang,Yingdong Yang,Fei Zhang,Xiangshu Chen
In recent years, membrane separation technology has received extensive attention in CO 2 /N 2 separation. Carbon nanotubes (CNTs) were regarded as ideal fillers for constructing high permeability mixed matrix membranes (MMMs) due to their special tubular structure. However, the interfacial compatibility between CNTs and organic polymer phases is a large challenge, seriously hindering the development of carbon-based mixed matrix membranes. In this work, we proposed a novel polyethyleneimine (PEI) surface functionalization strategy to effectively improve the compatibility between multi-walled carbon nanotubes (MWCNTs) and Pebax-1657. The as-prepared PEI@MWCNTs/Pebax-1657 MMMs were analyzed by XRD, EDS, FTIR, TG, etc. The PEI can improve the compatibility of MWCNTs with the polymer matrix. In addition, the abundant amino groups in the PEI structure can provide ample active sites for CO 2 , which can improve CO 2 permeability and CO 2 /N 2 selectivity simultaneously. Combining the low resistance of MWCNTs to gas transport, the membrane showed 178.08% enhancement in selectivity (82.06) of CO 2 /N 2 compared to the pristine membrane with 152.49% increment in the permeability (150.51 Barrer) of CO 2 . This work provides a novel strategy for preparing carbon-based mixed matrix membranes with high gas separation performance.
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