Molecular Catalysis
·
2026
·
IF 4.3
Hairen Tang,Shiyang Qin,Xiu Yu,Jiamiao Lu,Yubin He,Xudong Xiao,Haojie Song,Yanhong Zhang,Baojiang Jiang
Electron-rich CNNS and electron-deficient COFV induce a built-in electric field via Fermi-level equilibration. • PEI improves interfacial contact and strengthens charge transfer. • A metal-free Type-II heterojunction enables efficient directional charge migration. • Exceptional CO 2 photoreduction is achieved in pure water without sacrificial agents or metals. The development of efficient metal-free photocatalysts is of great importance for advancing solar-driven CO 2 conversion. Graphitic carbon nitride (g-C 3 N 4 ) has attracted extensive attention due to its unique electronic structure and excellent stability; however, its photocatalytic efficiency is severely limited by rapid photogenerated charge carrier recombination. Herein, we construct a metal-free COFV/CNNS heterojunction by exploiting the electronic disparity between electron-rich carbon nitride nanosheets (CNNS) and an electron-deficient π-conjugated covalent organic framework (COFV). A polyethyleneimine (PEI)-mediated surface modification strategy is employed to regulate interfacial assembly and enhance interfacial contact between the two components. The intimate heterointerface induces interfacial charge redistribution driven by the intrinsic electronic disparity between CNNS and COFV, leading to the formation of a built-in electric field at the interface through Fermi-level equilibration and electronic coupling. This internal electric field, together with the strong interfacial interaction, promotes efficient separation and directional migration of photogenerated charge carriers, thereby suppressing recombination and significantly enhancing photocatalytic performance. The optimized COFV/CNNS-60 composite exhibits a CO evolution rate of 14.8 times that of pristine CNNS and 3.9 times that of COFV under visible-light irradiation (λ ≥ 420 nm) in pure water without any sacrificial agents. This work provides a general strategy for constructing high-performance metal-free photocatalysts via interfacial electronic regulation and interface engineering, offering new insights into sustainable solar-to-fuel conversion. Download: Download high-res image (407KB) Download: Download full-size image
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Nano Materials
·
2026
·Vol. 9
·期 29
·13860-13868
·
IF 5.8
Li Bingshuang,Li Xin,Huang Xiaoxi
The
electrochemical CO 2 reduction reaction (CO 2 RR)
to produce multicarbon products represents a promising route
for sustainable carbon utilization. Copper-based catalysts are unique
in catalyzing C–C coupling, but the active Cu + species,
which favor ethylene formation, are prone to reduction during reaction.
In this work, we demonstrate that halogen doping, combined with a
nanoconfinement strategy, effectively stabilizes Cu + within
a nanoporous carbon matrix. Two model catalysts supported on porous
carbon spheres (Cu@C-1 derived from CuCl 2 and Cu@C-2 from
CuSO 4 ) were synthesized. After calcination, Cu@C-1 predominantly
comprises CuCl while Cu@C-2 mainly consists of Cu 2 O with
trace sulfur doping. They both have a similar average copper oxidation
state. During the CO 2 RR at −1.3 V versus the RHE,
the Cu@C-1 nanocatalyst achieves selective ethylene production with
a Faradaic efficiency (FE) of 41.5% and a partial current density
of 110.7 mA cm –2 whereas the Cu@C-2 nanocatalyst
primarily generates methane (FE of 49.5% and partial current density
of 124.4 mA cm –2 ). In situ and postreaction characterizations
reveal that nanoscale confinement in Cu@C-1 maintains its CuCl phase
under the reaction conditions, which promotes the *COCHO intermediate
and facilitates C–C coupling toward ethylene. Conversely, Cu@C-2
nanoparticles are reduced to metallic Cu 0 , favoring the
methane pathway. This work highlights that tailoring the precursor
anion offers a precise level of control over the initial copper phase
and its dynamic state under electrolysis, thereby steering the CO 2 RR selectivity toward the desired products.
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2026
·
IF 19.7
Boyang Zhang,Zhiyong Zhang,Yangfan Li,Yangqi Wei,Xingmiao Huang,Chuncheng Chen,Hua Sheng,Jincai Zhao
Post-synthetic strategy modularly integrates CO 2 -to-CO and CO-to-C 2+ sites. • Redox mediator and confinement synergize to regulate cascade reactions. • Confined TEMPOL acts as PCET mediator, lowering CO 2 -to-*COOH barrier. • Inactive MOF is transformed into an efficient CO 2 -to-C 2+ electrocatalyst. Efficient electrochemical conversion of CO 2 to multi-carbon (C 2+ ) products requires the integration of two sequential functionalities: CO 2 activation to *CO and subsequent CO-initiated C-C coupling. Conventional strategies typically rely on the rigid, pre-designed incorporation of these two functional units during catalyst synthesis. In contrast, we propose a post-synthetic modification strategy that introduces a molecular CO 2 activation unit into a pre-formed catalyst scaffold, thereby enabling its spatially proximal coupling with intrinsic CO reduction sites. This concept is demonstrated by encapsulating 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL) into the pores of a tetrapyrazolylporphyrin copper-based metal–organic framework (FICN-8). Owing to the well-matched molecular dimensions, the confined TEMPOL and adjacent Cu nodes cooperatively define a cavity that spatially accommodates a CO 2 molecule. Reduced TEMPOL acts as a proton-coupled electron transfer (PCET) mediator, while spatial confinement regulates the local reaction environment, jointly lowering the free energy barrier for *COOH formation. The confined *COOH intermediate is subsequently converted to CO and further undergoes C–C coupling. As a result, FICN-8—originally inactive for CO 2 -to-C 2+ conversion (Faradaic Efficiency, FE< 0.6%)—is transformed into an efficient electrocatalyst, delivering a C 2+ Faradaic efficiency of 42.6% with a two-orders-of-magnitude enhancement in C 2 H 4 formation rate. Download: Download high-res image (123KB) Download: Download full-size image
✓ 已验证
产品关联
DOI
高影响因子
Frontiers in Energy
·
2025
·
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.
✓ 已验证
产品关联
DOI
高影响因子
Carbon Capture Science & Technology
·
2025
·
IF 10.5
Jia Song,Long Shi,Jing Wei,Min Deng,Zikang Qin,Lin Yang,Junfeng Zheng,Wenju Jiang,Lu Yao,Zhongde Dai
Axial coordination engineering is a promising method to regulate the active sites of single atom catalysts (SACs) in Electrochemical reduction of CO 2 (ECR) and further realize the manipulating of the electrocatalytic activity, selectivity, and stability of catalysts. Here, a facile post-synthetic modification strategy of metal exchange and heteroatom dopant was proposed to develop a single iron atom catalyst coordinated with four planar N atoms and one axial Br atom (denoted as Fe x -NCBr y ) for ECR to CO. By altering the operating conditions including pyrolysis temperature as well as dopant amount of Fe and Br, the optimized Fe 20 -NCBr 0.3 catalyst acquired more surface-active sites and lower impedance, exhibiting an enhanced CO selectivity of 93.78% with a CO reduction current density of -21.16 mA cm −2 at -0.9 V (vs. RHE). This work provides fresh possibilities for tuning the SACs coordination environment with an axial heteroatom for improved ECR performance.
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Ziyan Liu,Junrong Chen,Yuanlan Wang,Wenqing Zhang,Wenlei Wang,Jing Wang
The photocatalytic reduction of CO 2 to CO is often constrained by suboptimal visible-light harvesting, interfacial recombination losses, and durability under repeated cycling. Here we design a Bi–BiOBr@CNF architecture that integrates metallic Bi (for plasmon-assisted excitation and interfacial electron transfer), oxygen/bromine vacancies (for CO 2 adsorption/activation), and a conductive CNF network (for dispersion and transport). Photoelectrochemical characterizations elucidate the synergistic mechanism. Under visible light, the catalyst delivers CO as the single detectable product with high selectivity; cycling tests reveal performance decay that is mechanistically linked to defect evolution, and a moderate-temperature regeneration restores activity. The results elucidate the respective roles of Bi 0 , O V , Br V , and the CNF scaffold within an integrated mechanistic framework, and indicate a viable strategy for durable photocatalytic reduction of CO 2 to CO.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Yanni Lang,Dongfeng Hong,Rongze Ma,Haoqiang Zhang,Liang Xu,Xinye Zhao,Dan Wu,Yongjin Li,Dacheng Zhou,Zhiguo Song,Yugeng Wen,Yong Yang,Jin Han,Jianbei Qiu
The construction of chiral materials has always been a research hotspot in the field of non-chiral nanomaterials. By introducing chiral destructive agents, materials are endowed with chiral nanostructures, which can be used in the field of photocatalysis. Au nanoparticles (Au NPs) are a typical photosensitizer capable of producing surface plasmon resonance (SPR) effects, producing CO and CH 4 in photocatalytic CO 2 reduction. We suggest that the SPR effect of the photocatalyst (D-BiOBr/Au) for Au NPS deposition of nonchiral bismuth bromide oxide nanomaterials can enhance the photocatalytic CO 2 reduction by enhancing spin-polarized electrons. It is worth noting that D-BiOBr/Au chiral materials enhance spin-polarized electrons due to SPR effect, and their photocatalytic CO 2 reduction performance is significantly better than D-BiOBr and original BiOBr without SPR effect. The CO yield of D-BiOBr/Au is 24.39 μmol/g h −1 , which is 2.02 times of D-BiOBr and 2.43 times of BiOBr, respectively. The mechanism of photocatalytic CO 2 reduction was further studied by FDTD simulation. The reason for the improved photocatalytic CO 2 reduction efficiency of D-BiOBr/Au is the increase of spin-polarized electrons due to the SPR effect, thus prolonging the carrier lifetime and promoting spin-polarized electron-hole separation. The results show that enhancing spin-polarized electrons through SPR effect is an effective strategy to improve photocatalyzed CO 2 reduction in photocatalyzed semiconductors.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2025
·
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
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF SUPERCRITICAL FLUIDS
·
2025
·
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.
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
·
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.
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
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.
✓ 已验证
产品关联
DOI
高影响因子
ChemSusChem
·
2026
·Vol. 19
·期 1
·e202501680
·
IF 6.6
Jinlong Wu,Haiqiang Mu,Min Zhu,Xueru Zhao,Ting Zhang,Jiaxin Bai,Jin Zhang,Feng Li,Jing Li
Copper-based catalysts offer promise for CO 2 -to-C 2+ conversion but suffer from instability of Cu + species, which are active sites critical for enabling C−C coupling. In this work, we synthesized Lanthanum (La)-doped Cu x O (La-Cu x O) catalysts with varying La/Cu ratios to investigate how the interplay between doping-induced electronic effects and grain boundary (GB)-driven stabilization affects deep CO 2 reduction to C 2+ . Combined density functional theory calculations and in situ spectroscopic characterization reveal that the unique 4f orbital configuration and strong Lewis acidity facilitate charge transfer of La, stabilizing Cu + during CO 2 reduction reaction (CO 2 RR), while simultaneously inducing lattice distortion to increase GB density. This modulation preserves Cu + /Cu 0 interfaces while enhancing *CO dimerization kinetics. Furthermore, La doping boosts *CO coverage at GB-rich regions and lowers the C−C coupling barrier. The optimized La-Cu x O-2 catalyst (La/Cu = 0.224) achieves a 45.2% C 2 H 4 Faradaic efficiency (FE) and 75.4% C 2+ FE at −0.8 V RHE , with partial current densities of 87.5 and 146.7 mA cm −2 , respectively, surpassing undoped Cu x O. Remarkably, it retains more than 90% initial activity after 24 h operation, demonstrating exceptional stability. This work provides a rational strategy for stabilizing Cu + and tailoring pathways via rare-earth doping. Graphical La doping stabilizes Cu + /Cu 0 interfaces via electronic modulation and lattice distortion, enhancing grain boundary density in Cu x O catalysts for efficient CO 2 electroreduction. The optimized La-Cu x O-2 achieves 75.4% C 2+ Faradaic efficiency and 146.7 mA cm −2 partial current density at −0.8 V versus reversible hydrogen electrode, suppressing hydrogen evolution and enabling scalable CO 2 -to-C 2+ conversion.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）