JOURNAL OF CATALYSIS
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2025
·
IF 6.5
Mingming Chu,Wenjing Sun,Songbing Yu,Yuanhang Li,Fangyu Zhu,Lijuan Yu,Yongyong Cao,Xuebo Cao,Yiming Li
Covalent organic frameworks (COFs) that incorporate heterocycles featuring multiple nitrogen atoms, such as triazine, bipyridine, and heptazine, are seen as promising heterogeneous photocatalysts for CO 2 photoreduction, while the substantial effect of N-atom relative locations in this transformation has rarely been systematically studied. Herein, a collection of isostructural porphyrin-based COF catalysts bearing bipheyl, 2–2′-bipyridine and 3–3′-bipyridine are judiciously designed for CO 2 photoreduction under simulated sunlight irradiation (1000 W/m 2 ). As results, comparing with the frequently used biphenyl and 2–2′-bipyridine unit, the porphyrin COF incorporating 3–3′-bipyridine yields a significant enhancement in photoelectric properties, and the CO production rate of 3–3′-Bpy-COF is 2 and 10 times higher than that of 2–2′-Bpy-COF and Bp-COF. Insights on the origin of the improved photocatalytic activity and reaction mechanism are further investigated, revealing above tiny variation of N sites results in a larger dipole moment for the 3–3′-Bpy-COF, facilitating the separation and transfer of photogenerated excitons. Moreover, The X-ray Photoelectron Spectroscopy (XPS) and Density Functional Theory (DFT) calculations reveal that the 3–3′-bipyridine N-atoms can strategically adjust the electron density surrounding the M−N4 active center of porphyrins, which stabilize the *COOH intermediate and reduce the energy barrier of the rate-determining step. This work highlights the collaborative influence of porphyrin and the steric location of N atoms within COFs photocatalysts for CO 2 reduction reaction, offering a new insight to design COFs endowed with exceptional capabilities for photocatalysis.
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高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Da Wang,Guangbo Liu,Chuanhui Zhang,Chao Feng,Jinhu Wu,Song Chen,Wenjie Xiang,Hao Huang,Zhihao Liu,Noritatsu Tsubaki
The reasons for the too high CO2 selectivity (near 50 C %) in Co2C-based Fischer–Tropsch to olefins (FTO) are not clear. Water–gas-shift (WGS) side reaction is thought to be responsible for this, but in-depth research is lacking. Here, we revealed the mechanism of the too high CO2 selectivity in Co2C-based FTO. Kinetic studies showed that WGS reaction was more likely to occur than the hydrocarbon production reaction. In addition, a too severe WGS reaction would result in the formation of an H2-enriched and CO-deficient environment on the catalyst surface, which was not favorable for the generation of light olefins. Catalyst characterization results proved that the severe WGS reaction could also lead to the transformation of prismatic Co2C to spherical Co2C. Theoretical calculations demonstrated that prismatic Co2C (020) and Co2C (101) facets were dominant crystal facets for both FTO and WGS reactions. Furthermore, in situ diffuse reflectance infrared Fourier transform spectroscopy experiments found that the H2O produced in FTO completely participated in the WGS reaction. This clearly revealed why the CO2 selectivity was close to 50 C % in FTO. Therefore, we believed that accelerating the desorption of H2O on the catalyst surface and preventing its readsorption are the key elements for inhibiting CO2 formation in FTO.
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ACS Catalysis
·
2025
·
IF 13.1
Shaorong Deng,Chenji Zhu,Xiuzhong Fang,Xianglan Xu,Xiang Wang
A series of Ru-x%Li+/SiO2 catalysts (x = 0.05–0.2), modified with varying amounts of lithium cation (Li+), were prepared via coimpregnation and evaluated for CO2 methanation to explore Li+ modification on Ru/SiO2. Introducing trace Li+ markedly boosts reaction activity, with the optimal Ru-0.1%Li+/SiO2 exhibiting 38.4 and 12.3 times higher overall reaction rate and turnover frequency at 200 °C, respectively, compared to Ru/SiO2. Structural characterization confirmed that Li+ incorporation effectively suppresses RuO2 crystallization, thereby improving Ru dispersion from 9.1% to 31.5%, enhancing the active surface area from 33 to 115 m2 g–1, while simultaneously reducing Ru particle size from 18.4 to 3.2 nm. In situ spectroscopy and surface reaction experiments revealed that the CO* pathway occurs for CO2 methanation on both catalysts, which involves CO2 dissociation and subsequent CO* hydrogenation. The smaller Ru nanoparticles on Ru-0.1%Li+/SiO2 exhibit superior intrinsic activity for both steps compared to the larger nanoparticles on Ru/SiO2. The additional alkaline sites introduced by Li+ additives also promote CO2 dissociation. The exceptional activity of Ru-0.1%Li+/SiO2 for CO2 methanation is governed by the synergistic effect between the Ru particle size effect and Li+-induced basicity, with the former being predominant.
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RSC Advances
·
2025
·Vol. 15
·期 17
·13313-13322
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IF 4.6
Hengxin Ren,Xinyu Sun,Tong Li,Zhixin Ren,Chaoyu Song,Yuguang Lv,Ying Wang
Herein, a new Z-scheme BiVO4/Cu2O/PPy heterostructure photocatalyst was developed with bismuth nitrate and ammonium vanadate as the precursors and sodium dodecyl benzyl sulfonate as the soft template. Through the spatial confinement effect of the sodium dodecyl benzyl sulfonate soft template, peanut-like BiVO4 and the BiVO4/Cu2O/PPy heterojunction were synthesized. The best performance was observed for BiVO4/Cu2O/PPy (5%), and its photodegradation rate was 6.57 times higher than that of pure BiVO4. The mechanism study showed that a light hole (h+), superoxide radical (·O2−), and hydroxyl radical (·OH) participated in the CO2 reduction process, which was different from the pure BiVO4 reaction system. Therefore, the proposed approach provides a new method for applying BiVO4/Cu2O/PPy photocatalysts and developing the same type of heterojunction photocatalyst, and they have effective practical application for environmental remediation.
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PubMed
高影响因子
Minerals
·
2025
·Vol. 15
·期 5
·506
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IF 2.2
Xiaoyu Li,Jie Chen,Wenqing Zhang,Chenyu Wang,Hui Ma,Kang Peng,Zheng Zhou
The urgent need for efficient CO2capture technologies has driven research into amine-functionalized adsorbents, though existing methods face trade-offs between adsorption capacity and cycling stability. This study addresses these limitations by developing a novel hybrid modification strategy combining chemical grafting and physical impregnation on polymorphic kaolinite minerals. Through systematic acid leaching and hybrid grafting–impregnation amine functionalization, the adsorbents with hierarchically porous structures and optimized performances are synthesized. The tubular adsorbent (ATK-APTES-PEI) demonstrated exceptional performance, achieving a CO2uptake of 1.68 mmol/g at 75 °C under a 60% CO2/40% N2mixed gas flow, with only 5.3% capacity loss after 10 adsorption–desorption cycles, significantly outperforming both rod-like (ARK-APTES-PEI, 1.55 mmol/g) and flake-like (AFK-APTES-PEI, 1.23 mmol/g) variants. The unique pore structure of ATK-APTES-PEI enables simultaneous high amine loading and maintained gas diffusion pathways, while the hybrid modification strategy synergistically enhances both adsorption capacity and stability by increasing active surface sites. These findings establish critical structure–property relationships for mineral-based adsorbents and demonstrate a scalable approach for industrial CO2capture applications. The work provides a blueprint for designing cost-effective, stable adsorbents using abundant clay minerals, bridging materials science with environmental engineering for sustainable carbon management solutions.
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MOLECULES
·
2021
·Vol. 26
·期 17
·5293
·
IF 4.412
Like Ouyang,Jianfei Xiao,Housheng Jiang,Shaojun Yuan
CO2adsorption in porous carbon materials has attracted great interests for alleviating emission of post-combustion CO2. In this work, a novel nitrogen-doped porous carbon material was fabricated by carbonizing the precursor of melamine-resorcinol-formaldehyde resin/graphene oxide (MR/GO) composites with KOH as the activation agent. Detailed characterization results revealed that the fabricated MR(0.25)/GO-500 porous carbon (0.25 represented the amount of GO added in wt.% and 500 denoted activation temperature in °C) had well-defined pore size distribution, high specific surface area (1264 m2·g−1) and high nitrogen content (6.92 wt.%), which was mainly composed of the pyridinic-N and pyrrolic-N species. Batch adsorption experiments demonstrated that the fabricated MR(0.25)/GO-500 porous carbon delivered excellent CO2adsorption ability of 5.21 mmol·g−1at 298.15 K and 500 kPa, and such porous carbon also exhibited fast adsorption kinetics, high selectivity of CO2/N2and good recyclability. With the inherent microstructure features of high surface area and abundant N adsorption sites species, the MR/GO-derived porous carbon materials offer a potentially promising adsorbent for practical CO2capture.Keywords:nitrogen-doped;porous carbon;melamine resin;graphene oxide;CO2adsorption
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高影响因子
SCIENCE OF THE TOTAL ENVIRONMENT
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2021
·
IF 7.963
Wei Yi,Diweina Zheng,Xianhua Wang,Yingquan Chen,Junhao Hu,Haiping Yang,Jingai Shao,Shihong Zhang,Hanping Chen
In this study, batched hydrothermal experiments on corn stalk were conducted at 240–330 °C under CO 2 or inert (N 2 ) atmosphere. The distribution and characteristics of gaseous, solid, and liquid products were analyzed in detail to comprehensively investigate the effects of CO 2 on the hydrothermal conversion of biomass, especially on the cellulose and lignin in biomass. The results demonstrate that compared with N 2 , CO 2 slightly increased the liquid and gas yields and significantly improved the control effect of temperature on bio-oil components. Under CO 2 atmosphere, bio-oil achieved effective enrichment of ketones and phenols at 240 °C and 300 °C, respectively, and their highest relative contents reached 44.8% and 62.0%, respectively. In addition, the hydrochar obtained under CO 2 atmosphere showed higher crystallinity , which is conducive to its subsequent utilization. This study explored the feasibility of introducing CO 2 into the biomass hydrothermal process to realize the high-value utilization of biomass waste and the reuse of CO 2 .
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高影响因子
ENERGY & FUELS
·
2018
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IF 3.024
Na Rao,Mei Wang,Ziming Shang,Yanwen Hou,Guozhi Fan,Jianfen Li
Modifications by impregnation and grafting are commonly used for the preparation of amine-functionalized MCM-41. A comprehensive evaluation of the advantages and disadvantages of the two methods was performed in this work. MCM-41 was synthesized by the hydrothermal method, setting the amine-loading mass fraction at 40, 50, and 60 wt %. Three amine-modified adsorbents were prepared by impregnating polyethylenimine (PEI), and the three other adsorbents were prepared by grafting 3-aminopropyltriethoxysilane (APTS) onto MCM-41. The as-prepared adsorbents were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, and N2 adsorption–desorption techniques. CO2 adsorption capacities were measured, and the experimental data were fitted with adsorption kinetic models. The cyclic stability of the adsorbents prepared by the two kinds of amine-modified methods was compared using the cyclic adsorption–desorption experiments. The characterization results showed that the target adsorbents were prepared successfully. The thermal stability of the adsorbents modified by grafting was better than the thermal stability of the adsorbents modified by the impregnation. Maximum CO2 adsorption capacities of 3.53 mmol g–1 (50% PEI–MCM-41) and 2.41 mmol g–1 (50% APTS–MCM-41) could be reached at 25 °C and 1 atm, which were 4.7 and 3.2 times greater than that of MCM-41. The Avrami model fitted the experimental data well, indicating a variety of interactions between the adsorbents and CO2. CO2 adsorption capacity after 5 adsorption–desorption cycles decreased by 14.22 and 5.19% for the adsorbents prepared by impregnation and grafting, respectively. It was concluded that MCM-41 modified by impregnation and grafting followed the same kinetic model. The absorbents modified by impregnation showed higher CO2 adsorption capacity and amine-loading efficiency, while those prepared by grafting had better thermal and cyclic stabilities.
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ACS Applied Energy Materials
·
2021
·
IF 6.024
Yangyang Wang,Xue Wang,Bingcheng Ge,Jianxin Guo,Carlos Fernandez,Qiuming Peng
The Li–CO2 battery is a potential energy storage device that not only possesses a theoretical energy density as high as 1876 W h kg–1 but also alleviates the consumption of fossil resources by converting the greenhouse gas CO2 into electric energy. However, some technique bottlenecks, such as high overpotential, low recyclability, and low energy density, severely prohibit its application rhythm. Here, we prepare a binder-free MXene–MnO2 composite film using vacuum-assisted filtration and in situ reduction, which can be used as a freestanding cathode for Li–CO2 batteries. This MXene–MnO2 film electrode bestows good cycle stability (∼220 cycles), high specific capacity, and lower overpotential (∼0.89 V) in Li–CO2 batteries. Both experimental tests and first-principles calculations reveal that the enhanced electrochemical properties are associated with three aspects. First, the MXene–MnO2 film offers a high electrical conductivity and porous structure, which provide fast transport channels for electrons and ions. Then, the replacement of Mn by Ti increases the adsorption of Li ions, which facilitates the rapid decomposition of Li2CO3. Finally, the synergistic effect of MXene and MnO2 exposes a large number of active sites, which increases the capacity of Li–CO2 batteries. Therefore, this self-supporting strategy on the MXene composite paves a way to develop high-performance Li–CO2 batteries.
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JOURNAL OF SOLID STATE CHEMISTRY
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2020
·
IF 2.726
Ding Guo,Cheng Li,Juan Zhang,Genyan Liu,Xiaogang Luo,Fengshou Wu
The chemical fixation of carbon dioxide to afford value added chemicals under solvent free and ambient conditions has gained considerable attentions. In this work, we successfully synthesized the porphyrin-based porous organic framework (PPOPs) through Schiff base reaction using 5,10,15,20-tetra(4-aminbiphenyl) porphyrin (TAPP) and 4,4′-biphenyldicarbaldehyde (BDA) as starting materials, which was then coordinated with cobalt to yield related metal complex (Co-PPOPs). The chemical structure and morphology of Co-PPOPs were characterized by absorption spectrum , FT-IR, X-ray photoelectron spectra (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and nitrogen physisorption . Co-PPOPs showed excellent catalytic activity towards the conversion of carbon dioxide to cyclic carbonates under ambient conditions. Furthermore, Co-PPOPs was recovered easily and could be used repeatedly (more than five times) without losing any catalytic activity. Thus, the as-prepared Co-PPOPs was a promising heterogeneous catalyst for carbon dioxide conversion, providing high turnover number than the previously reported catalysts.
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JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS
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2022
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IF 4.383
Adil Raza,Azhar Ali Haidry,Jaffer Saddique
Efficient solar to chemical energy conversion by promising semiconductor-based photocatalysis has gained huge interest due to being a potential solution for environmental remediation and energy problems. Though, the inadequate photogenerated charge separation practically limits the photocatalytic efficiency. Herein, mesoporous g-C 3 N 4 (CN) nanosheets coupled Cu 2 ZnSnS 4 (CZTS) hybrid composite as visible-light-driven photocatalyst is synthesized by a facile in situ hydrothermal self-assembly method and investigated for CO 2 photocatalytic reduction. The hybrid composite shows a slight red shift to the visible region with enhanced optical absorption . Under visible light irradiation, experimental results exhibit CZTS-CN hybrid composite has CO/CH 4 yield rates of 12.01/3.76 μmol g −1 after 5h, which are 1.54/1.41 times higher in comparison with bare CN. The heterojunction formation between CZTS and g-C 3 N 4 is restraining the electron-hole recombination and improves the photocatalytic performance. Finally, acceptable underlying mechanisms for CO 2 photocatalytic reduction over CZTS-CN hybrid composite are proposed. This work may inspire readers to provide sufficient guidance to design high-performance photocatalysts.
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ChemCatChem
·
2020
·Vol. 12
·期 19
·4825-4830
·
IF 4.853
Xiao Zhang,Kai-Hong Chen,Zhi-Hua Zhou,Liang-Nian He
Graphical Heterogeneous silver catalysis : Well-defined reduced graphene oxide supported Ag nanoparticles are developed for CO 2 conversion. This catalyst is efficient and reusable for various CO 2 utilization processes. Xiao Zhang, Kai-Hong Chen, Zhi-Hua Zhou, Liang-Nian He* Reduced Graphene Oxide Supported Ag Nanoparticles: An Efficient Catalyst for CO 2 Conversion at Ambient Conditions A highly efficient carboxylative cyclization of propargylic alcohols with CO 2 under atmospheric pressure catalyzed by silver (0) nanoparticles decorated reduced graphene oxide (Ag-rGO) is reported. Ag-rGO was fully characterized by scanning electron microscope spectra (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectra, Raman spectra and X-ray photoelectron spectroscopy (XPS). Notably, Ag-rGO can be also applied to the construction of other value-added chemicals (β-oxopropylcarbamates and 2-oxazolidinones) from CO 2 at ambient conditions. In addition, Ag-rGO is stable and reusable, which shows the potential for the practical application for CO 2 capture and utilization (CCU).
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