ChemSusChem
·
2019
·Vol. 12
·期 12
·2740-2747
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IF 7.804
Xiaoli Jin,Chade Lv,Xin Zhou,Liqun Ye,Haiquan Xie,Yue Liu,Huan Su,Biao Zhang,Gang Chen
Graphical Triple boost ! The high abundance of oxygen vacancies in Bi 24 O 31 Cl 10 play the following three roles for fully optimizing the CO 2 conversion efficiency: (i) enhance charge density, (ii) improve separation of electron–hole pairs, and (iii) lower energy for the formation of intermediates during the process. Unearthing an ideal model to describe the role of defect sites for boosting photocatalytic CO 2 reduction is rational and necessary, but it still remains a significant challenge. Herein, oxygen vacancies are introduced on the surface of Bi 24 O 31 Cl 10 photocatalyst (Bi 24 O 31 Cl 10 -OV) for fine-tuning the photocatalytic efficiency. The formation of oxygen vacancies leads to a new donor level near the conduction band minimum, which enables a faster charge transfer and higher carrier density. Moreover, oxygen vacancies can considerably reduce the energy for the formation of COOH* intermediates during CO 2 conversion. As a result, the activity of Bi 24 O 31 Cl 10 -OV for selective photoreduction of CO 2 to CO is significantly improved, with a CO generation rate of 0.9 μmol h −1 g −1 , which is nearly 4 times higher than that of pristine Bi 24 O 31 Cl 10 . This study reinforces our understanding of defect engineering in Bi-based photocatalysts and underscores the potential importance of implanting oxygen vacancies as an effective strategy for solar energy conversion.
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
Science Bulletin
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2024
·
IF 18.8
Guanshun Xie,Le Liao,Jie Wang,Peng Zhang,Benhua Xu,Xiuqiang Xie,Chi Chen,Babak Anasori,Nan Zhang
Selective CO 2 -to-CO photoreduction is under intensive research and requires photocatalysts with tuned microstructures to accelerate the reaction kinetics. Here, we report CuInS 2 nanosheet arrays with sulfur vacancies (V S ) grown on the two-dimensional (2D) support of Ti 3 C 2 T x MXene for CO 2 -to-CO photoreduction. Our results reveal that the use of Ti 3 C 2 T x induces strong support effect, which causes the hierarchical nanosheet arrays growth of CuInS 2 and simultaneously leads to charge transfer from CuInS 2 to Ti 3 C 2 T x support, resulting in V S formed in CuInS 2 . The strong support effect based on Ti 3 C 2 T x is proven to be applicable to prepare a series of different metal indium sulfide arrays with V S . CuInS 2 nanosheet arrays with V S supported on Ti 3 C 2 T x benefit the photocatalytic selective reduction of CO 2 to CO, manifesting a remarkable over 14.8-fold activity enhancement compared with pure CuInS 2 . The experimental and computational investigations pinpoint that V S of CuInS 2 resulting from the support effect of Ti 3 C 2 T x lowers the barrier of the rate-limiting step of *COOH → *OH + *CO, which is the key to the photoactivity enhancement. This work demonstrates MXene support effects and offers an effective approach to regulate the atomic microstructure of metal sulfides toward enhancing photocatalytic performance.
研究领域:
材料科学
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环境科学
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化学
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DOI
PubMed
高影响因子
Coatings
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2022
·Vol. 12
·期 2
·233
·
IF 3.236
Shiyuan Liu,Botao Hu,Junkai Zhao,Wenjun Jiang,Deqiang Feng,Ce Zhang,Wei Yao
The electrocatalytic CO2reduction reaction (CO2RR) into hydrocarbon products is one of the most promising approaches for CO2utilization in modern society. However, the application of CO2RR requires optimizing state-of-the-art catalysts as well as elucidating the catalytic interface formation mechanism. In this study, a flower-like nano-structured Bi catalyst is prepared by a facile pulse current electrodeposition method wherein the morphologies could be accurately controlled. Interestingly, nano-structured Bi is inclined to generate Bi2O2CO3in the air and form a stable Bi2O2CO3@Bi interface, which could enhance the CO2adsorption and conversion. In-situ Raman spectroscopy analysis also proves the existence of Bi2O2CO3on the electrode surface. In a practical CO2reduction test by a flow-cell reactor, the Bi2O2CO3@Bi electrode delivers a high faradaic efficiency of the CO2to formate/formic acid (~90%) at −1.07 V vs. reversible hydrogen electrode (RHE) with no obvious decay during more than a 10 h continuous test. The introducing surface Bi2O2CO3in nano-structured Bi supports a promising strategy as well as facile access to prepare improved CO2RR electrocatalysts.Keywords:CO2reduction;bismuth;Bi2O2CO3;interface;formic acid
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
JOURNAL OF ALLOYS AND COMPOUNDS
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2020
·
IF 4.65
Wenhong Yang,Yujing Dong,Zhipeng Wang,Yuqin Li,Chunhui Dai,Dongwei Ma,Yu Jia,Zhen Yang,Chao Zeng
A series of Sn 2+ doped MgIn 2 S 4 photocatalysts were prepared via a facial hydrothermal method . The Sn dopants substitute the sites of Mg atom in MgIn 2 S 4 unit cell, but not alter the crystal structure, demonstrated by the results of XRD and XPS . Compared to pristine MgIn 2 S 4 , Sn-doped MgIn 2 S 4 samples exhibit significantly enhanced photocatalytic CO 2 reduction activity. With increasing the Sn dopant content, the CO 2 conversion rate first ascends, achieving the maximum rate at Sn-MgIn 2 S 4 -2 sample, and then decreases. After illumination for 4 h, the highest yield of CO and CH 4 for Sn-MgIn 2 S 4 -2 sample reaches about 3.35 and 3.33 times higher than that of pristine MgIn 2 S 4 . The theoretical results based on density functional theory calculations reveal that Sn doping in MgIn 2 S 4 tunes the band structure from the direct-transition of MgIn 2 S 4 to indirect-transition, diminishes band gap and extends the light absorption range, reduces the effective masses of holes and promotes the migration of photoinduced carriers. The experimental results also demonstrate the positive role of Sn dopant in accelerating the separation and transportation of charges, and improving CO 2 adsorption ability. This work systematically investigates and discusses the Sn 2+ doping effect in MgIn 2 S 4 on crystal structure, lattice variations, electronic band structures , CO 2 adsorption ability, and photocatalytic CO 2 reduction activity, which can provide a new hint for the fabrication of efficient photocatalyst by metal ion doping.
研究领域:
材料科学
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环境科学
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化学
✓ 已验证
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
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2025
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IF 2.5
Zhile Xiong,Yuewen Chen,Weidong Xie,Jiali Huang,Xiaoli Zhang,Xiya Zhang,Hai Liu
The electrocatalytic reduction of CO2 using renewable electricity offers a sustainable approach for the production of valuable chemicals. However, this process is often hindered by low catalytic activity and poor selectivity. In this study, we have developed a novel electrocatalyst that integrates ZIF-8-regulated ZnO interfaces, undercoordinated surface sites, and mesoporous nanostructures. This design enabled the ZnO/ZIF-8 catalyst to achieve excellent CO2 conversion performance, with a CO2 Faraday efficiency of more than 91% over the potential range of -1.0 V to -1.6 V and a high current density compared to reversible hydrogen electrodes. At the optimal potential of -1.4 V, the CO Faraday efficiency reaches 95.57%, accompanied by a current density of -8.16 mA/cm2. The porous nature and superior CO2 adsorption ability of the ZIF-8 shell layer foster an optimal setting for CO2 conversion while enhancing the exposure of active sites. Additionally, the synergistic coupling of ZnO and ZIF-8 interfaces fine-tunes the electronic structure of the active sites, thereby enhancing CO2RR efficiency.
研究领域:
材料科学
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电化学
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产品关联
DOI
高影响因子
ChemSusChem
·
2024
·
IF 7.5
Chen Liao,Hongwei Zhou,Shunxin Zhang,Feng Wang,Ya Liu,Liejin Guo
Graphical A highly effective photocatalytic system (V Cu −CuInS 2 /MXene) was developed for transforming CO 2 into acetate under full spectrum irradiation. The incorporation of the LSPR effect and defect engineering leads to a highly selective system. Photocatalytic CO 2 conversion towards C 2+ fuels is a promising technology for simultaneously achieving carbon neutrality and alleviating the energy crisis. However, this strategy is inefficient due to the difficulty of both multi-electron transfer and C−C coupling during C 2+ formation. In this work, CuInS 2 /MXene heterostructure with Cu vacancy is rationally designed by in situ hydrothermal synthesis. The V Cu −CuInS 2 /MXene heterostructure has a suitable band structure and tight interface contact. Catalytic performances under different testing conditions, in situ spectroscopy, and COMSOL simulation reveal that LSPR-activated MXene promotes the formation of crucial intermediate CH 2 * and triggers the C−C coupling process under near-infrared light, as the key to acetate. Moreover, in situ XPS analysis, DFT calculations, and photoelectrochemical characterizations unveil that copper vacancy can promote charge transfer from CuInS 2 to MXene and boost local electron aggregation on the MXene, further enhancing the photocatalytic efficiency and selectivity of C 2 products. Contributing to the synergistic effect of copper vacancy and plasmonic MXene, V Cu −CuInS 2 /MXene achieved excellent CO 2 RR activity with an acetate evolution rate of 250.0 μmol/h/g and a selectivity of 97.5 % under the full spectrum irradiation, which is 38.8 and 3.3 times higher than that of V Cu −CuInS 2 and CuInS 2 /MXene, respectively.
研究领域:
材料科学
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环境科学
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化学
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DOI
PubMed
高影响因子
Nano Research
·
2017
·Vol. 10
·期 10
·3396-3406
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IF 7.354
Zhu Yuzhen,Gao Chao,Bai Song,Chen Shuangming,Long Ran,Song Li,Li Zhengquan,Xiong Yujie
Photocatalytic reduction of CO 2 into high value-added CH 4 is a promising solution for energy and environmental crises. Integrating semiconductors with cocatalysts can improve the activities for photocatalytic CO 2 reduction; however, most metal cocatalysts mainly produce CO and H 2 . Herein, we report a cocatalyst hydridation approach for significantly enhancing the photocatalytic reduction of CO 2 into CH 4 . Hydriding Pd cocatalysts into PdH 0.43 played a dual role in performance enhancement. As revealed by our isotopic labeling experiments, the PdH 0.43 hydride cocatalysts reduced H 2 evolution, which suppressed the H 2 production and facilitated the conversion of the CO intermediate into the final product: CH 4 . Meanwhile, hydridation promoted the electron trapping on the cocatalysts, improving the charge separation. This approach increased the photocatalytic selectivity in CH 4 production from 3.2% to 63.6% on Pd{100} and from 15.6% to 73.4% on Pd{111}. The results provide insights into photocatalytic mechanism studies and introduce new opportunities for designing materials towards photocatalytic CO 2 conversion.
研究领域:
材料科学
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环境科学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2016
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IF 8.328
Min Jiang,Yilin Gao,Zhaoyu Wang,Zhengxin Ding
Spinel CuCo 2 O 4 nanoplates were synthesized through a solvothermal method coupled with a calcination treatment in air. The prepared CuCo 2 O 4 samples were fully characterized by diverse physical and chemical techniques including powder X-ray diffraction (XRD), field emission scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and N 2 sorption measurement. The CuCo 2 O 4 material was developed as an efficient, low-cost and stable cocatalyst to boost photochemical CO 2 conversion with Ru(bpy) 3 2+ as a homogeneous photosensetizer. The catalytic performance of the CuCo 2 O 4 samples was evaluated toward visible-light-driven deoxygenative reduction of CO 2 to CO under mild conditions. Various parameters of the reaction system and the synthesis conditions of CuCo 2 O 4 were investigated and optimized to maximize the catalytic performance of CO 2 reduction system. The stability and the reusability of the CuCo 2 O 4 cocatalyst were examined. Moreover, the CuCo 2 O 4 cocatalyst was further proved to be highly active to promote CO 2 photoreduction catalysed by CdS semiconductor as a heterogeneous light harvester, and markedly reinforced photocatalytic CO 2 reduction performance was achieved.
研究领域:
材料科学
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环境科学
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化学
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DOI
高影响因子
Catalysis Science & Technology
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2021
·Vol. 11
·期 20
·6742-6749
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IF 6.119
Zuoyu Yan,Xiuxiu Wang,Yang Tan,Aihua Liu,Fenqiang Luo,Miaorong Zhang,Lingxing Zeng,Yan Zhang
Metals and their alloy-based electrocatalysts continue to attract considerable attention for electrochemical carbon dioxide reduction reactions (CO2RRs). In this work, cuprous oxide (Cu2O) was supported on N-doped flexible roughed graphite paper (NGP) to fabricate Cu2O/NGP self-supporting electrocatalysts for CO2RRs by electrodeposition and heat treatment. In the Cu2O/NGP electrocatalyst, NGP acted as a current collector and conducting channel, which can effectively transfer electrons from the active sites of Cu2O to NGP, and thus, enhance the catalytic performance of Cu2O/NGP for CO2RRs. The overall Faradaic efficiency of Cu2O/NGP for CO2RRs reached 96% at −0.9 V vs. reversible hydrogen electrode, of which 35% originated from yielding ethylene (C2H4), suggesting its high activity and C2H4 selectivity. Furthermore, the excellent stability of Cu2O/NGP over 10 h made it preferable as an effective electrocatalyst for CO2RRs. The good electrocatalytic performance could be attributed to the unique self-supporting structure and the synergetic effect between Cu2O and NGP.
研究领域:
材料科学
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电化学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
·
IF 16.744
Shanshan Qiao,Yuqing Chen,Yanhong Tang,Jili Yuan,Jiachao Shen,Danyu Zhang,Yi Du,Ziru Li,Dingwang Yuan,Haifang Tang,Chengbin Liu
Cu 2 O is promising to catalytically convert CO 2 into C 2 products by overcoming the instability and slow multi-electron transfer. Regulating catalytic construction and interface microenvironment is challenging to stabilize Cu 2 O and selectively convert CO 2 to C 2+ hydrocarbons. A photocatalyst (Cu 2 O@Cu-CN) of oxygen vacancy–rich Cu 2 O@Cu symbiont embedded in N -doped carbon skeleton is achieved by ligand competition strategy. The Schottky junction and the hydrophobic microenvironment in the catalyst together stabilize the active site against the Cu 2 O redox reaction. The hydrophobic interface can make the catalyst favorable for trapping CO 2 . The asymmetric interface with oxygen vacancy can enhance the adsorption and activation of CO 2 and *CO, thus reducing the energy barrier for the formation of *OCCO intermediates and promoting the coupling conversion of *OCCO to C 2 H 4 . The C 2 H 4 evolution rate reaches 46.27 μmol C2H4 g cat -1 h −1 with a high selectivity of 40.3 % using triethanolamine (TEOA) as a sacrificial agent, and the apparent quantum yield (AQY) is as high as 14.41 % (λ = 420 nm). The C 2 H 4 evolution rate is 2.10 μmol C2H4 g cat -1 h −1 in water without TEOA. Moreover, the productive rate of C 2 H 4 still maintains 95.37 % after lasting 20 h, showing a robust long − term stability.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Juzhi Leng,Xinru Yang,Qi Zeng,Wenting Chen,Shupeng Guo,Min Zhong,Lili Liu,Yunlei Chen,Pengju Yang,Mingqi Li
Photochemical reduction of CO 2 (CO 2 RR) to syngas is an attractive approach for carbon–neutral recycling. Manipulating binding strength to reactive species on catalyst surfaces is challenging but essential for achieving efficient syngas production with a desired CO/H 2 ratio. Here, we demonstrate that the binding strength to key reaction intermediates (*CO 2 , *H and *CO) on the Co 3 O 4 surface can be fine-tuned by incorporating varying amount of Zn atoms. Dedicated experiments and theoretical simulations unveil that Zn doping allows for simultaneous control of both CO 2 adsorption/activation and the adsorption affinity of *CO on Zn-Co 3 O 4 catalysts, resulting in a significant enhancement in CO 2 to CO conversion. Moreover, Zn doping can alter the hydrophilicity of the catalyst surface, affecting the water adsorption behavior and adjusting the hydrogen evolution reaction (HER) activity. As a result, the CO/H 2 ratio can be readily tuned via varying the Zn doping level. This study presents an effective and economical method approach to manipulate the electronic structure of catalyst surfaces for controlling the kinetics of CO 2 RR and HER reactions, providing valuable insight into the design of highly active transition metal oxides (TMOs) based photocatalysts for syngas production with a tailored CO/H 2 ratio.
研究领域:
材料科学
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化学工程
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Inorganic Chemistry Frontiers
·
2024
·Vol. 11
·期 18
·6044-6051
·
IF 6.1
Kunhong Li,Yumei Hong,Xinyi Ma,Yujie Zhao,Shihao Zhang,Pengtao Ma,Jingyang Niu,Jingping Wang
Photocatalytic carbon dioxide reduction is considered an important strategy to solve environmental problems, such as greenhouse gases, but designing and synthesizing effective photocatalysts is a challenge. In recent years, photocatalytic carbon dioxide reduction by polyoxometalates (POMs) has attracted increasing research interest. Herein, the first purely inorganic ruthenium–germanium–molybdenum–oxygen cluster, Na12Rb2[Ru2O2(GeMo10O36)2]·44H2O (Ru2Ge2Mo20), was synthesized by hydrothermal and volatilization methods and applied to photocatalytic carbon dioxide reduction. The yield of CH4 reached 547.84 μmol g−1 in the heterogeneous photocatalytic reaction system with an electron selectivity of 96.86% with respect to CO (71.08 μmol g−1) after 6 h. The reaction mechanism was confirmed by UV-Vis diffuse reflection spectroscopy, ultraviolet photoelectron spectroscopy (UPS), electrochemical measurements, and steady-state fluorescence quenching experiments. This work provides a reference for the design of Ru-containing polyoxometalates for photocatalytic CO2 reduction.
研究领域:
材料化学
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环境科学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）