MOLECULES
·
2025
·Vol. 30
·期 12
·2573
·
IF 4.6
Jinliang Lin,Rongying Liao,Li Li,Shuli Yao,Shengkai Li,Yun Zheng,Fei Fei
Photocatalytic CO2conversion is one of the ideal approaches to address both topics of solar energy shortage and carbon neutrality. Cobalt(II) centers coordinated with bipyridines have been designed and evaluated as catalysts for CO2conversion under light irradiation. Herein, we report a series of pyridine-based cobalt complexes with alkyl substituents as molecular photocatalysts, aiming to elucidate the effects of alkyl type and substitution position on catalytic performance through spectroscopic and electrochemical measurements. The substitution of the hydrogen at 4,4′-positions on the bipyridine ring with a methyl group, a tert-butyl group, and a nonyl group led to a decrease in the conversion rate of CO2by 13.2%, 29.6%, and 98%, respectively. The methyl substituents at the 5, 5′-positions of the bipyridine ring resulted in a 71.1% decrease in the CO2conversion rate. The usage of either 6, 6′-Me2-2,2′-bipy, 2,4-bipy, or 3,3′-bipy resulted in no detectable activity for CO2conversion in the current system. Both photo- and electrochemical analyses have been employed to reveal the relationship between changing ligands and photocatalytic performance on the molecular scale. These results demonstrate that bulky ligands significantly hinder CO2reduction by cobalt complexes due to steric interference with coordination and active-site accessibility. This study demonstrates that the substituent effect of ligands on photocatalytic reactions for CO2conversion provides valuable insight into a deeper understanding of molecular catalysis.
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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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JOURNAL OF MOLECULAR STRUCTURE
·
2025
·
IF 4.7
Jiale Ni,Zicheng Yang,Binxuan Hong,Yi Feng,Jianfeng Yao
This research endeavors to optimize the morphology and edge defects of g-C 3 N 4 through straightforward pyrolysis of rationally chosen precursors, with the objective of increasing the CO 2 conversion efficiency. Our findings reveal that employing melamine and urea as precursors yields tubular g-C 3 N 4 (CN tube), featuring an increased surface area and a greater density of edge defects than melamine-derived bulk g-C 3 N 4 and urea-derived layered g-C 3 N 4 . As a result, the obtained CN tube can deliver an impressive yield of 98 % for CO 2 cycloaddition with epichlorohydrin at 12 h under mild conditions of 80 °C and 0.1 MPa CO 2 pressure, significantly outperforming those derived from melamine (53 %) or urea (66 %) alone. This investigation demonstrated the pivotal role of a tubular architecture and enriched edge defects in facilitating the thermally driven CO 2 fixation process to produce cyclic carbonates.
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ACTA PHYSICO-CHIMICA SINICA
·
2025
·
IF 13.5
Wenlong Wang,Wentao Hao,Lang He,Jia Qiao,Ning Li,Chaoqiu Chen,Yong Qin
S-scheme heterojunctions have garnered significant interest in photocatalytic CO 2 conversion to valuable products (e.g., CH 4 ) due to their enhanced charge separation and robust redox capabilities. Carbon dots (CDs), with their tunable band structures and light absorption ranges, show particular promise in constructing efficient S-scheme photocatalytic systems. Nevertheless, the critical roles of CDs' band alignment and surface adsorption properties in determining heterojunction configuration, charge carrier kinetics, and ultimately CO 2 activation/product selectivity distribution remain insufficiently explored. Herein, we construct four CDs/TiO 2 heterojunctions using CDs synthesized from varied carbon sources, in which S-scheme heterojunctions were successfully constructed based on cost-effective coal pitch (C-GQDs, 1.75 nm), glucose (G-CQDs, 1.84 nm), and acetone (CQDs-X, 1.82 nm) carbon sources, whereas Type-I heterojunctions were formed by carbon black based CDs (GQDs-A, 1.92 nm). Systematic investigations reveal that both the band structure and adsorption characteristics of CDs play important roles in the charge transfer path and separation efficiency, CO 2 adsorption and activation capacities, and product selectivity in photocatalytic CO 2 reduction. Remarkably, the introduction of CDs significantly broadens the photo-response range compared to fresh TiO 2 , and in particular, the C-GQDs/TiO 2 exhibits exceptional performance with a CH 4 production rate of 32.7 μmol·g −1 ·h −1 , surpassing TiO 2 by 6.3-fold and outperforming GQDs-A/TiO 2 , CQDs-X/TiO 2 , and G-CQDs/TiO 2 by factors of 3.8, 2.7, and 2.3, respectively. This heterojunction simultaneously achieves 72.6 % CH 4 selectivity and 98.1 % hydrocarbons selectivity (encompassing CH 4 , C 2 H 6 , C 2 H 4 , and C 3 H 8 ). In contrast, composites incorporating GQDs-A, CQDs-X, or G-CQDs exhibit substantially diminished CH 4 selectivity (<40.0 %). The high CH 4 production rate and selectivity of C-GQDs/TiO 2 can be attributed to its unique S-scheme heterojunction structure, higher reduction potential, and well-matched CO 2 and H 2 O adsorption and activation capabilities. This study provides unique insights into the efficient photoreduction of CO 2 to CH 4 driven by the S-scheme heterojunction electron transfer pathway in CDs/TiO 2 photocatalysts.
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ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Liuliu Zhong,Qisheng Hu,Changjian Li,Jing Ding,Chundong Zhang,Hui Wan,Lei Wang,Guofeng Guan
The hydrogenation of CO2 to produce α-olefins and other high-value chemicals plays a crucial role in energy transformation and sustainable low-carbon development. However, the CO2 hydrogenation pathway for α-olefin synthesis still encounters various challenges, such as limited CO2 conversion and low α-olefin selectivity. To tackle these issues, this study initially assessed the catalytic properties of iron-based catalysts with varying morphologies and particle sizes. The findings indicated that the spherical Fe3O4 catalysts with large specific surface area demonstrated high CO2 conversion (20.8%) and α-olefin selectivity (14.4%) To improve CO2 adsorption and facilitate carbon chain growth, K and Sr were introduced to modify the spherical Fe3O4 catalysts. The synergistic electronic and structural effects of K and Sr contributed to enhanced α-olefin formation. Experimental data revealed that, under reaction conditions of 340 °C, 2.5 MPa, and a space velocity of 5000 h–1, the optimized 5K10Sr/Fe3O4 microsphere catalyst achieved a CO2 conversion of 45.4%, C2+ selectivity of 68%, chain growth factor of 0.67, and LAO (linear α-olefins in C4+ products) selectivity of 53.6%.
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ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Xiongwei Tian,Zheng Chen,Francesco Iacoviello,Mengyin Xie,Wenqing Chu,Yuqun Zhuo
The electroreduction of carbon dioxide (CO2R) presents a promising avenue for mitigating CO2 emissions while producing valuable chemicals. In this work, we report a novel pressure equilibrium strategy tailored for pressurized CO2R in a zero-gap electrolyzer, aiming at accommodating the high-pressure CO2 sources from its capture, utilization, and storage scheme. We investigated the impact of pressure on the CO2R performance under both gaseous and supercritical conditions, while also examining the synergistic interplay of temperature with high pressure. Significant enhancement of energy efficiency (46.5%) with high CO Faradaic efficiency (94.4%) and low cell voltage (−2.72 V) was achieved at 200 mA/cm2 under 75 bar and 80 °C. In addition, we noticed that the agglomeration and migration of salt precipitation within the gas diffusion electrode were effectively suppressed under pressurized conditions, which indicated the potential benefit for prolonged cell stability.
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yifang Sun,Xiongwei Yang,Hao Zhou,Xinxin Zhao,Yao Shen,Jingkai Zhao,Jiexu Ye,Chenghang Zheng,Shihan Zhang,Xiang Gao
CO 2 emissions from industrial processes are becoming a growing global concern due to their impact on climate change. Catalyst-aided amine solvent regeneration is an effective approach for achieving low-energy carbon capture. Existing desorption catalysts regenerate amine solutions by accelerating proton transfer during CO 2 desorption, but limited proton transfer efficiency under alkaline conditions leads to inevitable deactivation of active sites. Herein, we developed TiO 2 /Ti 3 C 2 , a TiO 2 nano-islands structured catalyst via in situ oxidation of Ti 3 C 2 T x MXene nanosheets. The remaining MXene enhances electron transfer between TiO 2 nano-islands, promoting CO 2 desorption-induced solvent regeneration through proton-coupled electron transfer effect via Raman spectroscopy and low-temperature electron paramagnetic resonance experiments. Theoretical calculation demonstrates that TiO 2 /Ti 3 C 2 reduce the energy barrier of solvent regeneration by 44.9 % compared to the non-catalytic scenario. The CO 2 desorption rate increased by 150 %, while the relative energy penalty of the solvent regeneration decreased by 75 %. The regeneration temperature was reduced from 120 °C to 98 °C with an amine-based biphasic solvent, effectively preventing ~28 % of amine degradation. Additionally, TiO 2 /Ti 3 C 2 demonstrates exceptional stability, showing negligible performance degradation and structural changes after 10 cycles. This work offers valuable insights for designing catalysts to achieve efficient and robust CO 2 capture.
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NEW JOURNAL OF CHEMISTRY
·
2025
·
IF 2.5
Xiang Gao,Jiajia Zhao,Hao Song,Xintong Zhou,Yuehua Deng,Jiali Liu,Yanrui Li
Graphitic carbon nitride (CN), a promising photocatalyst for CO2 reduction, suffers from inefficient light harvesting and sluggish charge separation dynamics, which severely restricts its application. Ionic liquids (ILs) have been used for the assisted preparation of photocatalysts, thus effectively altering their geometric and electronic properties. Herein, the 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF6) IL was introduced as a modifier to successfully construct a P- and F-co-doped porous CN catalyst via simple calcination of the IL and urea without any organic solvents and templates. The optimized catalyst exhibited an enhanced photocatalytic activity for CO2 reduction via gas–solid mode under visible light irradiation, achieving CO and CH4 evolution rates of 39.9 and 2.63 μmol g−1 h−1 (CO selectivity of 94%), which were 7.8 and 4.8 times higher than those of pristine CN, respectively. PFCN also demonstrated excellent reusability and stability. Comprehensive characterization revealed that the strategy of doping of P and F atoms significantly enlarged the surface area, improved CO2 adsorption, broadened visible-light harvesting, and accelerated charge transfer and separation efficiency. This work highlights the potential of ILs as multifunctional agents for designing high-performance doped CN photocatalysts.
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Endian Hu,Li Lin,Kailun Chen,Jinglin Li,Jingwen Chang,Yukun Zhao,Jianguo Jiang
Controlling CO 2 emissions is paramount for mitigating global warming. Developing solid amine adsorbents with high CO 2 adsorption capacity using minimal active species is essential for advancing carbon capture technology. In this study, waste polystyrene foam was utilized as the raw material to synthesize waste-derived hyper-cross-linked polymer (WHCP) supports via Friedel-Crafts alkylation using different catalysts (FeCl 3 and AlCl 3 ). Polyethyleneimine (PEI) was then impregnated into the supports (WHCP/Fe and WHCP/Al) to prepare waste-derived resin-based solid amine adsorbents. The adsorption performance of these adsorbents was systematically evaluated under varying amine loadings (10–50 %) and temperatures (30–105 °C). Although WHCP/Fe possessed a larger specific surface area and pore volume, WHCP/Al exhibited a higher proportion of mesopores and macropores, which facilitated the loading of the bulky amine molecules of PEI. This resulted in PEI-modified WHCP/Al possessing a more favorable pore structure and improved amine dispersion. The PEI-modified WHCP/Al exhibited excellent adsorption performance and favorable kinetic characteristics, maintaining a prolonged rapid adsorption phase (1.62–2.47 min) and a high peak adsorption rate of 8.10 mmol CO 2 /(g·min), along with a stable and relatively short half-time. Herein, 50 %-WHCP/Al demonstrated superior adsorption performance, achieving an optimal CO 2 adsorption capacity of 3.00 mmol/g at 75 °C and maintaining high adsorption capacity across a broad temperature range. Furthermore, it exhibited a capacity decay rate of only 10.22 % after 10 adsorption-desorption cycles. This study provides a theoretical foundation for the recycling of waste polystyrene and application in cost-effective carbon capture technologies.
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JOURNAL OF POLYMER SCIENCE
·
2025
·
IF 3.6
Dake Zhang,Wenzhen Wang,Dengmeng Song,Xingang Jia,Dingyuan Deng,Jingyu Wang,Xinyi Wang,Li Xia
While organogel adsorbent resins demonstrate excellent performance in organic pollutant separation, their limited reusability and high carbon footprint significantly restrict further development and application. Addressing the urgent environmental challenge of CO 2 emissions, we leveraged the inherent biodegradability and eco-compatibility of CO 2 -derived poly(propylene carbonate) (PPC) to synthesize a series of highly crosslinked PPCG materials by incorporating glycidyl methacrylate (GMA)—a monomer featuring carbon–carbon double bonds, ester groups, and epoxy functionalities—during terpolymerization. The introduced ester groups facilitate chemisorption and enhanced diffusion of lipophilic organics. Studies confirmed PPCG's exceptional adsorption capacity for chloroform, benzene, toluene, and tetrahydrofuran (THF), achieving a remarkable 977% swelling ratio for chloroform. After 8 adsorption–desorption cycles, all PPCG variants (PPCG1–PPCG5) retained > 95% adsorption efficiency. Thermal and mechanical analyses further validated that increased crosslinking density improved material stability. This green, reusable organogel adsorbent addresses the critical gap in applying CO 2 -based polycarbonates to separation technologies, establishing a novel functionalization strategy for next-generation adsorbent design. Graphical Schematic illustration of the synthesis process and working mechanism of organic gel adsorption resin.
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Xiaohui Sun,Linglong Wang,Yongxiao Tuo,Bangyan Zhang,Tao Gan,Jiansong Miao,Chunming Xu
Renewable-driven electrochemical reduction of CO 2 (CO 2 RR) to syngas is an attractive approach to achieve carbon neutrality. However, high current density at specific H 2 /CO molar ratios is challenging. Herein, a sulfur, nitrogen co-doped carbon supported Ni an Co dual-atom-system is designed as electrocatalyst to produce syngas from CO 2 RR. By regulating the molar ratio of Co and Ni in the dual atom system, H 2 /CO molar ratios of 1 and 2 that are typically suitable for a downstream Fischer-Tropsch synthesis process can be controlled in a wide current density range from 50 to 250 mA/cm 2 . This is attributed to the fact that single Ni sites are highly active for CO 2 RR to CO, while single Co sites are highly active for H 2 production. Moreover, experiments combined with theory confirm the presence of a sulfur-bridged Co and Ni moiety in the dual-atom system, and electrons are transferred from the Co and neighboring Ni sites to the bridged S atom. These electron deficient Co and Ni sites efficaciously balanced the adsorption strength of COOH* and H*, further facilitating syngas production without scarifying total current densities. This study provides a useful case for the fabrication of dual-atom catalysts with industrial relevant syngas production via CO 2 RR.
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JOURNAL OF MOLECULAR STRUCTURE
·
2025
·
IF 4.7
Liang Ye,Siyang Jin,Ke Yang,Jianchao Zhou,Hang Wu,Yue Jiang,Wei Xu
A high-entropy lanthanide-based metal-organic framework (HE-LnMOF), integrating five distinct lanthanide ions (Eu 3 ⁺, Tb 3 ⁺, Gd 3 ⁺, Dy 3 ⁺, Ho 3 ⁺) and 2-aminoterephthalic acid (H 2 N-BDC) ligands, was solvothermally synthesized for efficient catalytic conversion of CO 2 into cyclic carbonates. Structural analyses confirmed the homogeneous distribution of lanthanide ions within the framework, inducing lattice distortion while preserving crystallinity. The material features uncoordinated amino groups acting as base sites and unsaturated metal centers serving as Lewis acid sites, synergistically enhancing CO 2 adsorption and activation. HE-LnMOF demonstrated superior catalytic performance for converting CO 2 into cyclic carbonates compared to monometallic Ln-MOF analogs. In situ DRIFTS studies revealed intensified carbonate intermediate signals, corroborating the role of cooperative acid-base sites in accelerating the reaction. This work demonstrates the potential of high-entropy design in MOFs to amplify catalytic efficiency and stability, offering a sustainable pathway for CO 2 utilization.
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