iScience
·
2025
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IF 4.1
Hong Qian,Binxia Yuan,Yuhao Liu,Li Wang,Rui Zhu,Pengyu Dong
TiO 2 has low photocatalytic activity due to its easy recombination of photogenerated charges and low visible light utilization efficiency. This study utilized the keto-enol tautomerism principle of fructose in an alkaline environment to successfully obtain Cu 2 O/TiO 2 (CT), Cu 2 O/TiO 2 /Cu (CTC), and TiO 2 /Cu (TC) catalysts. As Cu(I) transformed into Cu(0), the bandgap narrowed, significantly enhancing visible light absorption. Photocatalytic tests showed that CT-0.15 exhibited the highest hydrogen production rate (279.53 μmol g −1 h −1 ), which was 25.18 times higher than that of TC-2. However, CTC-1 had the highest CO production rate (10.58 μmol g −1 h −1 ). Optoelectronic test revealed that CT-0.15 and CTC-1 had higher separation efficiency of photogenerated exciton. Density functional theory (DFT) calculations indicated that the change in the valence state of Cu influenced the reaction mechanism, with CT being favorable for the adsorption of H + in HER and CTC promoting the adsorption of CO 2 in carbon dioxide reduction reaction (CO2RR).
研究领域:
材料科学
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环境科学
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DOI
PubMed
高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Haopeng Jiang,Xiaohui Yu,Jinhe Li,Lele Wang,Weikang Wang,Chunxia Wu,Liyong Tang,Qinqin Liu
Herein, a NH 2 -MIL-125(Ti)@Ag@AgCl (NM@Ag@AgCl) stacked core–shell heterojunction with Z-scheme carrier transfer mechanism was developed to fulfil the goal of synchronous reactions of CO 2 reduction and H 2 O oxidation. In detail, the NM@Ag@AgCl was obtained by in-situ loading the AgCl as the shell-inorganic semiconductor on the octahedral NM as the core-organic semiconductor, followed by in-situ transforming part of the AgCl shell into the plasmonic Ag nanoparticles using a photo-reduction method. As a result, the interface effects of core–shell architecture majorized by the Ag electronic mediator can favor the transmission of photogenerated carriers and reduce electron transport resistance; while the plasmonic Ag mediated Z-scheme mode with a giant internal electronic field provided a strong driving force to recombine the carriers with weak redox ability, reserving the carrier with strong redox ability on the NH 2 -MIL-125-core and AgCl-shell for the simultaneous reactions. The CO and H 2 O 2 yields of the optimal NM@Ag@AgCl were 6.02 and 5.43 μmol⋅g −1 ⋅h −1 , which were 3.31 and 4.02 times that of the NM, respectively. This study furnishes a novel thread for the design of core–shell organic–inorganic heterojunction with high interfacial charge transfer for realizing the simultaneous reactions.
研究领域:
材料科学
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环境科学
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化学工程
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DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2021
·Vol. 56
·期 19
·11426-11435
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IF 4.22
Yan Dong,Peng Zhen,Wang Wei,Zeng Peng,Huang Yiyin
Abstract Carbon-based metal-free catalysts exhibit great applications in electrochemical CO 2 reduction (ECR), while most studies merely focus on large-sized carbons with limited ratio of surface atoms for engineering to create surface active centers. Here, we report a joint treatment of C60 by heating and plasma to induce a dramatic performance promotion during ECR. The electrochemical measurements indicate the Faraday efficiency for ECR toward CO production kept at high level over 80% in a wide potential region from − 0.4 to − 0.7 V versus RHE, with the highest value reaching 96.8%. The physical characterization reveals that fragmentation of C60 occurs together with N/O doping, both of which could induce change in electron structure, causing the formation of *COOH intermediate and ultimately leading to the optimized activity and selectivity for CO production. This treatment route was further revealed to be applicative for other carbon materials, e.g., single-walled carbon nanotube, to promote its ECR activity and selectivity. Graphical Abstract
研究领域:
材料科学
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电化学
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DOI
高影响因子
ACS Applied Nano Materials
·
2023
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IF 5.9
Fengyu Tian,Mingzhao Zhu,Xuebiao Sun,Xuemin Yan
Selective CO2 photoreduction to valuable chemicals is promising for a carbon-neutral future and still remains a challenge. Herein, Zn vacancy-rich ZnO (Zn1–xO) nanoparticles were used as cocatalyst to construct a Zn1–xO/TiO2 nanostructure via the self-assembly process. The existence of Zn vacancies triggered the intimate contact between Zn1–xO and TiO2 through the Ti–O–Zn bonds. Theoretical and experimental results show that the hybridization of Zn1–xO and TiO2 resulted in the formation of a p–n heterojunction, leading to the enhanced separation efficiency of photoinduced electron–hole pairs. As a result, the optimized Zn1–xO/TiO2 nanocomposite exhibited nearly 100% selectivity of CO2-to-CO photoreduction, and the productivity was 4.2 times higher than that of pristine TiO2. In situ Fourier transform infrared spectra along with theoretical calculations were also conducted to investigate the mechanism of the selective photocatalytic CO2-to-CO process. It is concluded that the charge depletion on the TiO2 surface induced by the charge transfer from Zn1–xO to TiO2 can lower the energy barrier of CO* desorption and convert the endothermic CO* desorption process into an exothermic reaction step, thus triggering selective CO production. This work provides a new perspective on the rational fabrication of nanostructures for efficient and selective photocatalytic CO2 conversion through intermediate modulation.
研究领域:
材料科学
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化学工程
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环境科学
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DOI
高影响因子
Materials
·
2023
·Vol. 16
·期 20
·6665
·
IF 3.4
Manying Sun,Chuanwei Zhu,Su Wei,Liuyun Chen,Hongbing Ji,Tongming Su,Zuzeng Qin
Photocatalytic CO2reduction is a tactic for solving the environmental pollution caused by greenhouse gases. Herein, NH4H2PO4was added as a phosphorus source in the process of the hydrothermal treatment of melamine for the first time, and phosphorus-doped hollow tubular g-C3N4(x-P-HCN) was fabricated and used for photocatalytic CO2reduction. Here, 1.0-P-HCN exhibited the largest CO production rate of 9.00 μmol·g−1·h−1, which was 10.22 times higher than that of bulk g-C3N4. After doping with phosphorus, the light absorption range, the CO2adsorption capacity, and the specific surface area of the 1.0-P-HCN sample were greatly improved. In addition, the separation of photogenerated electron–hole pairs was enhanced. Furthermore, the phosphorus-doped g-C3N4effectively activated the CO2adsorbed on the surface of phosphorus-doped g-C3N4photocatalysts, which greatly enhanced the CO production rate of photocatalytic CO2reduction over that of g-C3N4.
研究领域:
环境科学
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材料科学
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产品关联
DOI
PubMed
高影响因子
Catalysis Science & Technology
·
2021
·Vol. 11
·期 10
·3422-3427
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IF 6.119
Yuqing Shao,Xinkui Wang,Zhaolin Dou,Xiaoyu Liang,Xinxin Zhang,Min Pang,Qiang Xu,Min Ji,Min Wang
Solar-driven CO2 conversion into fuels and sustainable energy has attracted increasing attention around the world. However, the efficiency of the transformation remains relatively low due to the rapid recombination of photogenerated charge carriers. In this work, we prepared a ZnIn2S4–ZnAlOx nanocomposite for visible light driven CO2 reduction. The thin layered structure facilitated the photoinduced charge carrier separation and transfer, and also gave excellent adsorption ability towards CO2 molecules. Such a nanocatalyst exhibited excellent activity in visible-light driven CO2 reduction with a CO optimal formation rate of 1100 μmol g−1 h−1, which is 5 times that over bulk ZnIn2S4, and the CO/H2 ratio was increased from 0.2 over bulk ZnIn2S4 to 1.5 over the ZnIn2S4–ZnAlOx composite. In situ FT-IR experiments indicated that CO2 was reduced on ZnIn2S4–ZnAlOx following a COOH* pathway. This work gives insights into the mechanism of the photocatalytic CO2 reduction reaction and inspiration to construct novel heterostructure materials for application in energy and environmental catalysis.
研究领域:
材料科学
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环境催化
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光化学
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能源转化
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DOI
高影响因子
Catalysis Science & Technology
·
2024
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IF 4.4
Sisi Lin,Xinkui Wang,Xiaoyu Liang,Xinxin Zhang,Min Wang
Photocatalytic reduction of CO2 to high value-added chemicals and fuels has received widespread attention. However, the higher thermodynamic stability of CO2 greatly limits its conversion efficiency. Frustrated Lewis pairs (FLPs) have been well-established to be very effective in CO2 activation. In this work, we prepared ZnIn2S4–AlOOH (ZIS–AlOOH) composites for visible-light-driven CO2 reduction. The Lewis basic OHv sites on the AlOOH surface (one H removed from OH) and an adjacent Lewis acidic unsaturated Al site (Al3+unsatur.) form the FLPs. The composite structure facilitated light absorption, CO2 adsorption activation, and separation of photogenerated carriers, thus improving the CO2 photoreduction activity (CO generation rate of 510.3 μmol g−1 h−1), and suppressing hydrogen evolution with the CO/H2 ratio increasing from 0.38 for ZnIn2S4 (ZIS) to 0.84 for ZIS–AlOOH. This work elucidates a rational strategy for the construction of efficient photocatalysts and provides insight into the mechanism of the photocatalytic CO2 reduction reaction.
研究领域:
材料科学
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环境科学
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化学工程
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DOI
高影响因子
Nature Communications
·
2022
·Vol. 13
·期 1
·1-11
·
IF 17.694
Shangguan Wenchao,Liu Qing,Wang Ying,Sun Ning,Liu Yu,Zhao Rui,Li Yingxuan,Wang Chuanyi,Zhao Jincai
Achieving CO 2 reduction with H 2 O on metal photocatalysts and understanding the corresponding mechanisms at the molecular level are challenging. Herein, we report that quantum-sized Au nanoparticles can photocatalytically reduce CO 2 to CO with the help of H 2 O by electron-hole pairs mainly originating from interband transitions. Notably, the Au photocatalyst shows a CO production rate of 4.73 mmol g −1 h −1 (~100% selectivity), ~2.5 times the rate during CO 2 reduction with H 2 under the same experimental conditions, under low-intensity irradiation at 420 nm. Theoretical and experimental studies reveal that the increased activity is induced by surface Au–O species formed from H 2 O decomposition, which synchronously optimizes the rate-determining steps in the CO 2 reduction and H 2 O oxidation reactions, lowers the energy barriers for the *CO desorption and *OOH formation, and facilitates CO and O 2 production. Our findings provide an in-depth mechanistic understanding for designing active metal photocatalysts for efficient CO 2 reduction with H 2 O.
研究领域:
化学
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材料科学
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环境科学
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催化
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF POWER SOURCES
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2020
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IF 8.247
Zhijie Wang,Tengfei Li,Qihao Wang,Anxiang Guan,Na Cao,Abdullah M. Al-Enizi,Lijuan Zhang,Linping Qian,Gengfeng Zheng
Silver-containing material is one of the efficient electrocatalysts in converting CO 2 into CO , but competing hydrogen evolution reaction (HER) in aqueous solutions results in poor energy efficiency. Here, Ag 3 subnanoclusters with the structure sensitive to CO 2 activation are in situ prepared by the cyclohexene oxidation . Hydrophobically modified Ag nanomaterials with an average particle size from 1.0 to 3.3 nm are water-repulsive, organic-soluble, and composited of the Ag 3 cluster units, possessing the electron donation and strong chemical adsorption of CO 2 . In the electroreduction of CO 2 , a high mass activity about 10,200 A cm −2 g Ag −1 is achieved for CO production at −1.4 V vs. reverse hydrogen electrode (RHE) on Ag nanoclusters with the external size of 1.9 nm, exhibiting 20 times higher than commercial Ag nanoparticles (diameters of 60–120 nm). Electrochemical tests in flow cells show an excellent mass activity of 55,000 A cm −2 g Ag −1 with a large current density of around 30 mA cm −2 for the CO production at −0.71 V vs. RHE, much higher than the previously reported Ag catalysts. Hydrophobically made Ag 3 subnanoclusters facilitate the CO 2 electroreduction to CO in aqueous solutions through accelerating the electron donation and suppressing the side reaction of water reduction.
研究领域:
材料科学
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电化学
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纳米技术
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催化
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产品关联
DOI
高影响因子
COMBUSTION AND FLAME
·
2023
·
IF 4.4
Du Wang,Zhen-Yu Tian,Zhi-Hao Zheng,Wang Li,Ling-Nan Wu,Jiu-Jie Kuang,Jiu-Zhong Yang
As a polar solvent , N, N-Dimethylformamide (DMF) is a potential source of volatile organic compounds during industrial processing. The potential energy surface and pressure-dependent rate coefficients of DMF primary and secondary thermal decomposition were theoretically investigated by automatic ab initio calculations. A singlet aminohydroxycarbene route generating CO is found to be the most energetically favored channel among the unimolecular initiation reactions with a tight transition state. A kinetic model was proposed for DMF pyrolysis prediction and validated against the speciation data newly obtained from synchrotron vacuum ultraviolet photoionization mass spectrometry in a flow reactor within 773 K–1048 K and literature data in a jet stirred reactor within 450 K–900 K at atmospheric pressure. Satisfactory agreements were obtained for the major intermediates and products, but the model failed to capture the formation of some oxygenated compounds, possibly due to the missing reaction pathway for bimolecular addition. During pyrolysis , DMF is mainly consumed by the hydrogen abstraction reaction as the relatively high C N bond energy hinders the barrierless homolytic cleavage. Unlike aldehydes where the carbonyl site is favored, H-abstraction from DMF methyl sites is prevalent, although the acylamino group readily undergoes decarbonylation and β-scission forming oxygenated and nitrogenous parts. Consequently, CO and HCN are the major pyrolysis products. Besides, by incorporating essential high temperature kinetics, extended validation was conducted against the available intermediate temperature autoignition delay times (1000–1350 K, 2 bar) and laminar burning velocity data, and the reason for the discrepancy between the model prediction and experiments was inferred according to the sensitivity analyses.
研究领域:
化学工程
·
物理化学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Xin-Ran Shi,Sai-Nan Guo,Ruoxi Zhang,Biao Yang,Hua Zou,Jie-Xin Wang
Metal–organic frameworks (MOFs) have emerged as pivotal materials for the photocatalytic reduction of CO2 to CO due to their exceptionally high surface areas and abundant active sites. However, most of the currently reported MOFs are confined to micropores (<2 nm), which limits adsorption/desorption and substance transport during photocatalytic CO2 reduction reactions. Herein, hierarchically porous MOFs (HP-MOF-74) were synthesized based on the assembly of MOF-74-Ni nanoparticles with different particle sizes (21, 42, and 85 nm) using spray-drying technology. The simultaneous enhancement of CO2 adsorption performance and photoelectroactivity was achieved in HP-MOF-74 due to the additional mesoporous structure formed by the nanoparticle stacking. The HP-MOF-74 exhibits 1.14–1.38 times improvement in the CO2 adsorption capacity compared to the corresponding initial MOF-74 nanoparticles (N-MOF-74). Meanwhile, the hierarchical architecture enhances photon utilization through improved light reflections and accelerates electronic transmission via additional mesopore pathways. These synergistic advantages collectively contribute to a 1.2–2.1 times enhancement in the CO generation rates of HP-MOF-74 compared with N-MOF-74 counterparts. Particularly, HP-MOF-74–42 nm demonstrated the highest CO production rate of 6.65 μmol h–1, outperforming most reported MOF-based photocatalysts. The construction of hierarchically porous MOFs provides a new idea for the design of highly efficient CO2 reduction photocatalysts.
研究领域:
材料科学
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环境科学
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化学工程
·
纳米技术
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Feng Yue,Mengke Shi,Cong Li,Yang Meng,Shuo Zhang,Lan Wang,Yali Song,Jun Li,Hongzhong Zhang
Directly capturing CO 2 in ambient air and converting it into value-added fuels using photocatalysis is a potentially valuable technology. In this study, Cu-porphyrin (tetrakis-carboxyphenyl porphyrin copper, CuTCPP) was innovatively anchored on the surface of TiO 2 (titanium dioxide) nanosheets to form an S-scheme heterojunction. Based on this, a photocatalytic reaction system for stably converting CO 2 in ambient air into value-added fuels at the gas–solid interface was constructed without addition of sacrificial agents and alkaline liquids. Under the illumination of visible light and sunlight, the evolution rate of CO is 56 μmol·g −1 ·h −1 and 73 μmol·g −1 ·h −1 , respectively, with a potential CO 2 conversion rate of 35.8 % and 50.4 %. The enhanced of photocatalytic performance is attributed to the introduction of CuTCPP, which provides additional active sites, significantly improves capture capacity of CO 2 and the utilization of electrons. Additionally, the formation of S-scheme heterojunction expands the redox range and improves the separation efficiency of photo-generated charges.
研究领域:
光催化
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材料科学
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环境科学
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化学
✓ 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）