CHEMICAL ENGINEERING JOURNAL
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2025
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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
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2025
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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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Frontiers in Energy
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2025
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IF 6.2
Zhong Bowen,Hu Chengwei,Sun Kaian,Yan Wei,Zhang Jiujun,Xie Zailai
The electrochemical CO 2 reduction reaction (CO 2 RR) provides a promising approach to mitigate the global greenhouse effect by converting CO 2 into high-value chemicals or fuels. Noble metal-based nanomaterials are widely regarded as efficient catalysts for CO 2 RR due to their high catalytic activity and excellent stability. However, these catalysts typically favor the formation of C1 products, which have relatively low economic value. Moreover, the high cost and limited availability of noble materials necessitate strategies to reduce their usage, often by dispersing them on suitable support materials to enhance catalytic performance. In this study, a novel metal-based support, zirconium phosphate Zr 3 (PO 4 ) 4 , was used to anchor ultrasmall palladium nanoparticles (pre-ZrP-Pd). Compared to the reversible hydrogen electrode, the pre-ZrP-Pd achieved a maximum Faradaic efficiency (FE) of 92.1% for ethanol at −0.8 V versus RHE, along with a peak ethanol current density of 0.82 mA/cm 2 . Density functional theory (DFT) calculations revealed that the strong metal-support interactions between the ZrP support and Pd nanoparticles lead to an upward shift of the Pd d-band center, enhancing the adsorption of CO* and promoting the coupling of CO and CO to produce ethanol.
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APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
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IF 21.1
Lifei Liu,Luyuan Zhang,Xiaorui Du,Pengfei Li,Ruonan Wang,Yang Deng,Xia An,Xu Wu
Photoreduction of CO 2 to alcohol offers a sustainable solution to the energy crisis. The unsatisfactory selectivity and activity are hindered by the poor adsorption of *CO and sluggish C-C coupling process kinetics. Herein, the dual-channel ligand-to-metal charge transfer (LMCT) pathways were constructed by coordinating an electron-donor Ferrocene (Fc) on Lewis acid L-Cu-MOF-74 to produce Fc-Cu-MOF-74, aiming to modulate the d-band center and electron density, as well as enhance the electron transfer efficiency. As catalyzed by Fc-Cu-MOF-74, the evolution rate of photoreduction of CO 2 to ethanol achieved 103.3 μmol∙g −1 ∙h −1 with a selectivity of 64.9 %, which is higher than that of Cu-MOF-74 and L-Cu-MOF-74. Photoelectrochemical studies reveal that the incorporation of the electron donor Fc on L-Cu-MOF-74 effectively accelerates the electron transfer efficiency, reduces the energy of the LMCT. In-situ FT-IR and theoretical calculations reveal that the chemisorption of *CO and subsequent C-C coupling process are accelerated on the Cu site of Fc-Cu-MOF-74, which exhibits appropriate Lewis acidity. This electron transfer strategy provides a new pathway for the construction of high-performance CO 2 reduction reaction photocatalysts.
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Journal of Environmental Chemical Engineering
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2025
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IF 7.2
Wensheng Wu,Lingzhi Huang,XiuShuai Guan,Xiaochao Zhang,Changming Zhang,Jinbo Xue
Photocatalytic reduction of CO 2 is a promising strategy for the conversion of high value-added chemicals, but the difficulty lies in the design of photocatalysts that combine high electron transfer efficiency, activity and stability. In this paper, the pore structure and the number of active sites of carbon spheres were modulated to promote the adsorption and reduction of CO 2 . MBZCSs-40 achieved a CO yield of 28.23 μmol g -1 for 8 h. N 2 adsorption and desorption and SEM confirmed the existence of a hierarchical pore structure. XPS showed that the ratio of the introduced pyridine nitrogen groups was well linearly correlated with the reducing properties and was hypothesized to be the main active centers. CO 2 adsorption isotherms revealed that MBZCSs-40 had the highest adsorption capacity of 1.86 g. In situ infrared detected that CO 2 was adsorbed on the nitrogen active sites and converted to CO 2 *, followed by the generation of the key intermediate COOH* in the presence of e - and H + . The moderate amount of nitrogen doping promoted micropores generation and thus exposed more active sites. Pyridine nitrogen enhanced the adsorption and activation of CO 2 and promoted the generation of COOH*. This study provides a new perspective for the design of nitrogen-doped metal-free photocatalysts.
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JOURNAL OF MATERIALS SCIENCE
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2025
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IF 3.9
Zhang Lei,Cao Xueting,Xin Qingping,Ding Xiaoli,Jin Huimin,Chen Hao,Chu Qingquan,Du Yifei,Huang Wei,Zhang Ruihua,Bao Shiya,Zhang Yuzhong
In this study, a top-down etching method is used to obtain MXene nanosheets with an accordion-like structure, and the surface of the MXene nanosheets is functionalized with 3-aminopropyltriethoxysilane to obtain functionalized MXene nanosheets (f-MXene), which is combined into polyethylene oxide (PEO) copolymer matrix for fabricating mixed matrix membranes (MMMs). The f-MXene nanosheets enhance the CO 2 /N 2 separation performance of membranes in multiple ways. Firstly, the accordion-like structure of f-MXene increases the channel for rapid gas transport. Secondly, the two-dimensional sheet-shaped material has a high aspect ratio, which effectively weakens the interaction between polymer chains and inhibit crystallization. This increases free volume for molecular transport and helps improve gas permeability. Thirdly, the amino group can react reversibly with CO 2 , improving reaction selectivity, and facilitates CO 2 transport. Therefore, the PEO/f-MXene membrane exhibits excellent CO 2 permeability and CO 2 /N 2 selectivity. To explore more efficient separation technology, the membrane separation performance at low-temperature is investigated. At − 20 °C, the PEO/f-MXene-3% membrane has a CO 2 permeability of 47.8 Barrer and a CO 2 /N 2 selectivity of 280.9, which is 576.9% higher than that at 35 °C, exceeding the latest upper bound. Graphical
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JOURNAL OF SUPERCRITICAL FLUIDS
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2025
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IF 4.4
Zhongfeng Geng,Mingyu Yan,Yongxin Feng,Huisheng Lv
Baicalein, which exhibits antioxidant activity and wogonin, with anticancer activity, can be extracted from Scutellaria baicalensis Georgi. Their similar structures pose a challenge to further isolation. Supercritical Fluid-Simulated Moving Bed (SF-SMB) can function as a large-scale green separation process based on the adsorptive difference between them. The adsorption data of baicalein and wogonin on ZorBax SB-CN column in supercritical carbon dioxide/methanol were determined using the Elution by Characteristic Points method and could be well fitted by Langmuir model. At lower temperature or lower density of mobile phase, the adsorption capacity increased, with the maximum being 70.10 kg/m 3 for baicalein and 45.25 kg/m 3 for wogonin. The diffusion coefficients of the baicalein and wogonin were determined by the Taylor-Aris peak broadening method. They decreased with higher pressure, lower temperature, or higher density of the mobile phase. This work offers basic data support for the design of SF-SMB systems and industrial platform technology.
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MACROMOLECULES
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2025
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IF 5.2
Shangzhong Zhang,Yixuan Xu,Panpan Li,Minghui Fan,Dejia Chen,Chengming Wang,Lifeng Yan
Polymerization of CO2 into polyurea under mild pressure and temperature is still a challenge, especially when using diamine from natural feedstocks. Herein, l-lysine is directly used as a diamine without derivatization and protection for capture and copolymerization of CO2 under mild temperatures and pressures (0.1–0.5 MPa, 60–90 °C) with the assistance of superbase 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Water-soluble lysine-polyurea (L-PU) has been synthesized. The weight-average molecular weight of L-PU reaches 3 × 104 g/mol, indicating the efficient reaction of lysine and CO2. In addition, NMR studies confirmed that the unprotected carboxyl acid group (−COOH) in L-PU remains more than 80%, and the polymer may be a candidate to replace nonbiodegradable polyacrylate acid (PAA). The free carboxyl acid group also provides a change to further derivatives of the L-PU. Interestingly, the water-soluble L-PU showed efficient fluorescence performance with quantum yield (QY) up to 20%, which may be attributed to the nonconventional intrinsic fluorescence of nonconjugated aliphatic polyureas containing heteroatoms. It allows the L-PU to be used for cell bioimaging, and in vitro studies reveal that the L-PU is biocompatible and can be efficiently endocytosed by cells with bioimaging ability, indicating that it may be a potential drug delivery system for imaging-guided treatment for cancer tissue.
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CHINESE JOURNAL OF CATALYSIS
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2026
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IF 17.2
Haonan Li,Wa Gao,Kangli Ma,Jian Lei,Olim Ruzimuradov,Akhtam Samiev,Ya Chen,Jingxiang Low,Yue Li
Cocatalyst loading has been extensively adopted in photocatalysis for enhancing photocatalytic performance. However, the sluggish interfacial charge dynamics between cocatalyst and photocatalyst has restricted the wide applications of such a strategy. Herein, we introduce the Ni–N interfacial bonds between lamellar nitrogen-vacancy-rich g-C 3 N 4 /CoNi 2 S 4 nanoparticles (CN-V N /CoNi 2 S 4 ) composite material to bridge the photogenerated charge carrier separation at their interface. Specifically, extended X-ray absorption fine structure analysis reveals that these Ni–N interfacial bonds are originated from the bonding of CoNi 2 S 4 with the nitrogen atoms adjacent to the nitrogen vacancies (V N ) in g-C 3 N 4 . Experimental evidence and theoretical calculations reveal that Ni–N interfacial bonds cannot only cause an intimate contact interface between CN-V N /CoNi 2 S 4 , but also modulate the charge distribution on the CN-V N and CoNi 2 S 4 , further boosting the photogenerated charge carrier separation. More interestingly, this tailored interfacial microenvironment significantly reduces the energy barrier for key intermediates formation while modulates the rate-determining step from *COOH generation to CO desorption, enabling efficient and controllable CO production. This work establishes a methodological framework for engineering advanced photocatalysts, enabling high-efficiency conversion of solar energy into clean fuels.
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ACS Applied Polymer Materials
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2026
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IF 4.7
Shuyi Li,Shiyuan Cheng,Jumei Wang,Xiaojing Xing,Xinfeng Cheng,Dongqin Bi,Dongfang Qiu,Nam Hoon Kim,Joong Hee Lee,Xuyang Li
Membrane separation technology has great potential for application in gas separation due to its environmentally friendly, efficient, and energy-saving advantages. Polyamide (PA) membrane is an ideal material for efficient separation of CO2 due to its high amine density and excellent CO2 affinity. This work presents a trio-modulated strategy that enhances the CO2 separation performance of PA membranes by modifying the substrate, optimizing the preparation method, and incorporating fillers. Substrate modification facilitates the interfacial polymerization of a polyamide layer on a polysulfone substrate. PA membranes fabricated via vapor–liquid interfacial polymerization typically exhibit a low defect density and superior CO2 separation performance. The incorporation of fillers (γ-cyclodextrin, namely γ-CD) can effectively loosen the microstructure of the PA membrane, and the CO2-philic groups of γ-CD fillers furtherly enhance the selectivity of CO2 through the facilitated transport mechanism. The prepared membranes display excellent CO2 separation performance with CO2/N2 selectivity of 479.5, CO2/CH4 selectivity of 395.9, as well as a CO2 permeance of 4179.8 GPU. The proposed strategy provides a facile and effective route to trio-modulated PA membranes for the study of CO2 separation and can provide a avenue for the development of advanced membrane materials for CO2 separation.
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Nature Communications
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2026
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IF 18.1
Zhu Kaili,Shou Weiqiang,Jia Bingquan,Song Yuxiang,Wang Tao,Sun Licheng,Zhang Biaobiao
Acidic electrochemical CO 2 reduction (CO 2 RR) typically requires K + ions to create a local H + -depleted microenvironment, suppressing competing hydrogen evolution reaction (HER). Excessive localized K + causes salt precipitation, compromising electrolysis stability. Achieving stable operation with high Faradaic efficiency (FE) at low K + concentrations remains a crucial challenge for conventional nanomaterials. Inspired by water-trapping function of sponges, we design a three-dimensional interconnected porous cubic SnO 2 electrocatalyst (SnO 2 sponge) that confines OH – within porous channels to consume proton influx from the bulk, enabling durable acidic CO 2 RR towards formic acid (HCOOH). Theoretical and experimental studies reveal the SnO 2 sponge sustains substantially higher OH – concentration than dispersed SnO 2 nanoparticles. At pH 1.82, the SnO 2 sponge achieves 94.5% FE HCOOH at 800 mA cm –2 . With only 0.075 M K + , it retains 95.2% FE HCOOH at 400 mA cm –2 . Notably, it enables continuous HCOOH production at 400 mA cm –2 with 97.7% FE HCOOH for over 390 h without cleaning. This work provides a promising strategy for durable and efficient CO 2 RR in acidic media with low K + concentrations.
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PubMed
高影响因子
Journal of the American Chemical Society
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2026
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IF 16.6
Yu Yang,Jun Wang,Yaohui Shi,Xue Han,Yuhang Wang,Biswaranjan Mohanty,Yongxiang Liang,Mianqi Xue,Jie Zeng,Tongliang Liu,Aoni Xu,Fengwang Li
Achieving precise control over reaction pathways in the electrochemical CO2 reduction reaction (CO2RR) is a central challenge. Silver, for instance, is widely recognized for its high selectivity toward carbon monoxide (CO). Here, we demonstrate a strategy to steer the selectivity of Ag away from CO and toward formic acid (HCOOH) by engineering the nanoscale structure of water at the electrode–electrolyte interface. Using a polymeric cation, poly(diallyldimethylammonium chloride) (PDDA), in an alkali-metal-cation-free, strongly acidic electrolyte, we create a hydrophobic interfacial environment that promotes weakly hydrogen-bonded, “free-like” water (f-H2O). Using operando spectroscopy and isotope labeling, we establish a direct, quantitative correlation between the abundance of f-H2O and HCOOH selectivity. Electrochemical analyses and theoretical simulations using density functional theory and ab initio molecular dynamics suggest that the f-H2O-rich environment opens a distinct mechanistic channel for HCOOH formation via a direct, energetically favorable *H + CO2 hydrogenation reaction, a pathway disfavored in conventional alkali-metal-cation-based electrolytes where strongly hydrogen-bonded water (h-H2O) facilitates the *COOH pathway to CO. These findings highlight that the tuning of interfacial water structure is powerful in overriding the intrinsic selectivity of a catalyst and rationally directing CO2RR pathways.
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