JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2025
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IF 9.7
Kun Liu,Junping Niu,Yijia Bai,Jianlei Qi,Limin Han,Ning Zhu,Ligang Yan
Ligand engineering has proven to be an effective strategy for tuning and controlling the microenvironment of coordinated metal centers, highlighting the critical bridge between the activity and structural features of catalysts during electrocatalytic CO 2 reduction reactions (eCO 2 RR). However, the limited availability of diverse organic ligands has hindered the development of novel high-performing electrocatalysts. In contrast, small organic molecules have been widely used in the fabrication of metal complexes due to their well-defined functionalities, low cost, and easy accessibility. Herein, functionalized small organic molecules were employed to prepare a new type of Bi-based heterogeneous molecular catalyst. These molecular catalysts enhance both electrical conductivity and catalytic activity for converting CO 2 to formate in the eCO 2 RR. The relationship between the structure and electrochemical performance of organic-functionalized Bi-based heterogeneous catalysts was thoroughly investigated. Comprehensive characterization and kinetic studies demonstrated that the functional groups of the organic molecules construct bond pathways for electron transfer and promote the transformation of the active phase from Bi to Bi 2 O 2 CO 3 . In-situ Raman spectroscopy reveal that the organic molecules remain intact during the structural reorganization, which is beneficial for the sustained generation of Bi 2 O 2 CO 3 active site during the eCO 2 RR process. Consequently, the organic functionalized Bi-based catalysts achieved a high formate Faradaic efficiency (FE HCOO - ) of 89.8 % and a high current density (j HCOO - ) of 40.0 mA cm −2 at a potential of −0.95 V vs. RHE in an H-type cell. This work establishes a novel strategy for creating active heterogeneous catalysts using small organic molecules, opening new avenues for the development of efficient electrocatalysts for CO 2 reduction.
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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DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
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IF 13.3
Haichuan He,Xiao Yu,Wei Wang,Liu Deng,Hao Zeng,Liqiang Wang,Ke Zeng,Jianhan Huang,Minghui Yang,You-Nian Liu
Bismuth-based materials have emerged as promising electrocatalysts for the electrochemical reduction of carbon dioxide (eCO 2 RR) to HCOOH. However, it remains challenges to meet the practical application requirements and identify the active sites of bismuth-based catalysts in eCO 2 RR. Herein, bismuthate (MBi 2 O 4 , M = Ca, Cu, Zn) derived nanosheet-like electrocatalysts with metal-modified edge defects are developed. During electrochemical processes, MBi 2 O 4 pre-catalyst undergoes surface reconstruction to expose more active Bi 0 sites and to form abundant metal-modified edge defects, which facilitate the modulation of charge state of adjacent Bi sites and improve the adsorption of *OCHO intermediate, thereby enhancing the selectivity of eCO 2 RR towards HCOOH. The Ca-modified defect-rich Bi catalyst exhibits a maximum HCOOH Faradaic efficiency of 94.3 % at an industrially relevant current density of 400 mA cm −2 , together with high stability/reproducibility of 55 h. This work proposes a new strategy for construction of Bi-based catalysts and explores its structural reconstruction mechanism during the electrocatalytic process, opening a new window for design of eCO 2 RR catalysts.
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
Materials Today Sustainability
·
2023
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IF 7.8
G. Yang,H. Sun,R. Liu,J. Shi,X. Tong
Heterogeneous catalytic and selective C–C bond cleavage is considered as the important way for the production of high valuable compounds from large-molecule-weight feedstock . In this article, a sustainable and efficient aerobic oxidative C–C bond cleavage of lignin models is developed with the bismuth-based solid catalyst. Therein, the flower-like Bi 2 O 2 CO 3 exhibits a high photocatalytic efficiency in the reaction medium combined of n-butanol and tetramethylammonium bromide. For example, the selective oxidative C–C bond cleavage of 1-phenyl-ethane-1, 2-diol has been successfully carried out, where the substrate conversion and the selectivity of benzaldehyde was 95% and 99%, respectively. The study exhibited that the amount of oxygen vacancies plays a significant role on the photocatalytic selective aerobic oxidative cleavage processes. Moreover, the selective aerobic oxidative C–C bond cleavage of different lignin models was investigated, and all the yields of corresponding products are more than 90% with this photocatalytic system. Furthermore, the used flower-like Bi 2 O 2 CO 3 can be recycled at least 5 times without the obvious decrease of catalytic activity .
研究领域:
催化化学
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环境科学
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
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IF 8.1
Zhaoxin Huang,Shasha Zhang,Pengfei Zhu,Ming Duan,Yuling Jiang,Yu Chen
The BiOIO 3 /Bi 2 WO 6 binary catalyst was prepared by hydrothermal method, and a Bi 0 /I − -BiOIO 3 /Bi 2 WO 6 all-solid-state Z-scheme heterojunction composite catalyst with Bi 0 deposition and I-doping was prepared by further reducing it with NaBH 4 as reducing agent. When the content of BiOIO 3 is 20 wt% and n(NaBH 4 ): n(BiOIO 3 + Bi 2 WO 6 ) = 0.3, Bi 0 /I − -BiOIO 3 /Bi 2 WO 6 has the best photocatalytic activity. Under the optimized reaction conditions (catalyst dosage 1.0 g/L, antibiotic initial concentration 20 mg/L), the degradation efficiency of oxytetracycline (OTC) reached 83.56 % after 60 min reaction under visible light, and its pseudo-first-order reaction rate constant was 0.02431 min −1 , which was 2.56 times and 3.94 times that of pure Bi 2 WO 6 and pure BiOIO 3 , respectively. The characterization results show that the main reasons for the improvement of the activity of Bi 0 /I − -BiOIO 3 /Bi 2 WO 6 are the formation of heterojunction in the catalyst, the surface plasmon resonance (SPR) effect generated by Bi 0 and the impurity energy level introduced by I-doping, which jointly promote the separation of photogenerated electron-hole pairs (e − -h + ) in the catalyst and enhance the absorption capacity of the catalyst to visible light. The intermediates produced during the reaction were analyzed by high performance liquid chromatography-mass spectrometry (HPLC-MS). Two possible pathways for the degradation of OTC by Bi 0 /I − -BiOIO 3 /Bi 2 WO 6 were proposed. Finally, the electron transfer mechanism of Bi 0 /I − -BiOIO 3 /Bi 2 WO 6 all-solid-state Z-scheme heterojunction was proposed based on the test results of Tauc-plot curve and M–S curve.
研究领域:
环境科学
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材料科学
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DOI
高影响因子
Journal of Energy Chemistry
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2024
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IF 14
Guan Wang,Shengtao Zhong,Xiaoqian Xiong,Jing Li,Fangyuan Wang,Li Huo,Daoxiong Wu,Xingqi Han,Zhitong Wang,Qi Chen,Xinlong Tian,Peilin Deng
Bismuth-based catalysts are highly promising for the electrochemical carbon dioxide reduction reaction (eCO 2 RR) to formate product. However, achieving high activity and selectivity towards formate and ensuring long-term stability remains challenging. This work reports the oxygen plasma inducing strategy to construct the abundant grain boundaries of Bi/BiO x on ultrathin two-dimensional Bi nanosheets. The oxygen plasma-treated Bi nanosheet (OP-Bi) exhibits over 90% Faradaic efficiency (FE) for formate at a wide potential range from −0.5 to −1.1 V, and maintains a great stability catalytic performance without significant decay over 30 h in flow cell. Moreover, membrane electrode assembly (MEA) device with OP-Bi as catalyst sustains the robust current density of 100 mA cm −2 over 50 h, maintaining a formate FE above 90%. In addition, rechargeable Zn-CO 2 battery presents the peak power density of 1.22 mW cm −2 with OP-Bi as bifunctional catalyst. The mechanism experiments demonstrate that the high-density grain boundaries of OP-Bi provide more exposed active sites, faster electron transfer capacity, and the stronger intrinsic activity of Bi atoms. In situ spectroscopy and theoretical calculations further elucidate that the unsaturated Bi coordination atoms between the grain boundaries can effectively activate CO 2 molecules through elongating the C–O bond, and reducing the formation energy barrier of the key intermediate (*OCOH), thereby enhancing the catalytic performance of eCO 2 RR to formate product.
研究领域:
材料科学
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电化学
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环境科学
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DOI
高影响因子
Journal of Energy Chemistry
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2024
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IF 14
Haichuan He,Congcheng Yang,Liu Deng,Li Luo,Yahui Jiang,Liqiang Wang,Yi Zhang,Minghui Yang,You-Nian Liu
CO 2 -to-formate electrosynthesis with high selectivity and stability has been a long-sought objective. Unfortunately, most catalysts undergo structural and valence state changes due to surface oxidation during operation or storage, resulting in decreased catalytic performance. Herein, we report a efficient and stable BiIn@Cu-foam electrode through the in-situ regeneration of Bi 0 active sites to renew the surface activation. The electronic structure of Bi site can be regulated by introducing In, thereby enhancing the adsorption strength of *OCHO. The optimized electrode exhibits over 90% FE formate at a wide potential window (−0.9–−2.2 V), and formation rate for 3.15 mM cm −1 h −1 . Especially, the electrode can maintain the high performance at continuously electrolysis for more than 300 h, or for more than 50 cycles, even repeated operation and storage for more than 2 years. This work provides a promising candidate and new insight to construct industrially viable stable Bi-based catalyst for formate electrosynthesis.
研究领域:
材料科学
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电化学
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能源转化
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产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
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2023
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IF 6.6
Dongze Lai,Mingyu Xie,Huawang Zhao,Xiaomin Wu,Bihong Lv,Guohua Jing
Electrochemical reduction of CO 2 into high-value chemicals, such as formic acid (HCOOH), is an important way to resource CO 2 . Interfacial effects through catalyst design are important to improve the ECO 2 RR performance of Bi-based catalysts. A Bi/ATO heterojunction catalyst was constructed. The current density and FE HCOOH of Bi/ATO were 20 mA cm −2 and 95%, respectively, at a potential of -0.97 V, respectively, compared with the reversible hydrogen electrode (RHE). In-situ cyclic voltammetry curves and Raman spectra showed that electron density change occurred between ATO and Bi during the ECO 2 RR process. This Interfacial electron effects increased the conversion of adsorbed CO 2 molecules to HCOOH by reducing the Interfacial resistance. Interfacial electron transfers also prevented the complete reduction of Bi by transferring electrons to ATO during the ECO 2 RR, which stabilized Bi-O structures. Bi-O improved the selectivity for HCOOH, probably by accelerating the formation of an *OCHO intermediate.
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
Small
·
2023
·Vol. 19
·期 10
·2206440
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IF 13.3
Jingrong Zhai,Ye Hu,Mengfei Su,Jiangwei Shi,Hang Li,Yezhi Qin,Feng Gao,Qingyi Lu
It is a substantial challenge to construct electrocatalysts with high activity, good selectivity, and long-term stability for electrocatalytic reduction of carbon dioxide to formic acid. Herein, bismuth and indium species are innovatively integrated into a uniform heterogeneous spherical structure by a neoteric quasi-microemulsion method, and a novel C@In 2 O 3 @Bi 50 core-shell structure is constructed through a subsequent one-step phase separation strategy due to melting point difference and Kirkendall effect with the nano-limiting effect of the carbon structure. This core-shell C@In 2 O 3 @Bi 50 catalyst can selectively reduce CO 2 to formate with high selectivity (≈90% faradaic efficiency), large partial current density (24.53 mA cm −2 at −1.36 V), and long-term stability (up to 14.5 h), superior to most of the Bi-based catalysts. The hybrid Bi/In 2 O 3 interfaces of core-shell C@In 2 O 3 @Bi will stabilize the key intermediate HCOO* and suppress CO poisoning, benefiting the CO 2 RR selectivity and stability, while the internal cavity of core-shell structure will improve the reaction kinetics because of the large specific surface area and the enhancement of ion shuttle and electron transfer. Furthermore, the nano-limited domain effect of outmost carbon prevent active components from oxidation and agglomeration, helpful for stabilizing the catalyst. This work offers valuable insights into core-shell structure engineering to promote practical CO 2 conversion technology.
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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产品关联
DOI
PubMed
高影响因子
Nature Sustainability
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2024
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IF 25.7
Kong Xiangdong,Ni Jie,Song Zhimin,Yang Zhengwu,Zheng Jiana,Xu Zifan,Qin Lang,Li Hongliang,Geng Zhigang,Zeng Jie
Hydroxylamine is an important nitrogenous feedstock for the chemical industry. Conventional hydroxylamine synthesis methods utilize ammonia as the nitrogen source and require harsh reaction conditions, leading to unfavourable environmental footprint. Here we develop a plasma-electrochemical cascade pathway (PECP) powered by electricity for sustainable hydroxylamine synthesis directly from ambient air and water at mild conditions. In the first step, the plasma treatment of ambient air and water delivers a nitric acid solution with a concentration of up to 120.1 mM. Subsequently, the obtained nitric acid is selectively electroreduced to hydroxylamine using a bismuth-based catalyst. The faradaic efficiency for hydroxylamine reached 81.0% at −1.0 V versus reversible hydrogen electrode. As a result, this PECP method achieves a high hydroxylamine yield rate of 713.1 μmol cm −2 h −1 with a selectivity of 95.8%. Notably, both steps of the PECP method are operated at room temperature. Overall, our work provides a viable approach for efficient hydroxylamine synthesis from simpler feedstock at milder conditions, contributing to the sustainability transformation of the chemical industry.
研究领域:
化学工程
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环境科学
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产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2020
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IF 6.215
Xiu-Hui Zhao,Qing-Song Chen,De-Huang Zhuo,Jian Lu,Zhong-Ning Xu,Chong-Min Wang,Jing-Xiao Tang,Shi-Gang Sun,Guo-Cong Guo
Electrochemical reduction of CO 2 is still far away from the practical application because of the stability of CO 2 and the diversity of reduction products. It is thus of great importance to further explore catalysts with high efficiency for CO 2 reduction to targeting products. Herein, for the first time, a hybrid of BiO x decorated with carbon thin layer is developed as high active electrocatalyst for CO 2 conversion, which is synthesized by pyrolysis using Bi MOF as precursor and sacrificial template. It is found that the as-prepared BiO x catalyst is enriched with oxygen vacancies stabilized by the decorated carbon thin layer. The oxygen vacancies enriched BiO x catalyst exhibits superior performance for CO 2 reduction to formate, achieving a maximum Faradaic efficiency of 89.3% and a maximum current density of 37.8 mA cm −2 . The thin carbon layer and oxygen vacancies improve the charge transfer of the catalyst and hence in favor of the high formate current density. The defects of oxygen vacancies play a vital role in CO 2 adsorption and activation and thereby further enhancing the electrocatalytic ability for formate production.
研究领域:
催化
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电化学
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材料科学
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环境科学
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DOI
高影响因子
APPLIED SURFACE SCIENCE
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2025
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IF 6.9
Mingliang Sun,Ao Sun,Hongwei Zhu,Ruyu Zhang,Xiaowei Jia,Yan Xing
Photocatalytic nitrogen fixation provides a sustainable alternative to the energy-intensive Haber–Bosch process, yet its efficiency is limited by poor N 2 solubility, weak adsorption, rapid charge recombination, and competing hydrogen evolution. reaction (HER). In this work, we introduce a synergistic interfacial strategy integrating Schottky junction construction and hydrophobic surface engineering to enhance photocatalytic N 2 fixation. Bi nanoparticles are in-situ anchored onto Bi 3 TiNbO 9 (BTNO) to construct Bi/BTNO Schottky junctions, facilitating directional electron transfer and accumulation at Bi active sites. Concurrently, surface hydrophobicity of Bi/BTNO is precisely tailored via 1-dodecanethiol modification, promoting N 2 enrichment at the reaction interface while effectively suppressing HER. The optimized 2C 12 S-1 % Bi/BTNO catalyst achieves an exceptional ammonia production rate of 25.83 μmol g -1 h −1 in pure water without sacrificial agents, outperforming pristine BTNO by 6.96-fold and unmodified Bi/BTNO by 2.85-fold. Photoelectrochemical measurements and in situ FTIR spectroscopy verify enhanced charge separation and an associative distal pathway for N 2 reduction. This work underscores the importance of interface microenvironment design in addressing kinetic and selectivity limitations, offering a versatile platform for efficient solar-driven nitrogen fixation.
研究领域:
材料科学
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光催化
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环境能源化学
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纳米催化
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表面科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
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IF 22.1
Yini Mao,Yong Jiang,Qiao Gou,Shengmei Lv,Zuyou Song,Yimin Jiang,Wenbin Wang,Ming Li,Lirong Zheng,Wei Su,Rongxing He
Urea is of great importance for the survival and development of mankind because of its advantages in effectively increasing crop yields. A novel carbon-supported indium-doped bismuth nanoparticles (Bi: 10 %In/C NPs) was prepared for the synthesis of urea via the co-activated reduction of nitrate and CO 2 with an average Faraday efficiency (FE) of 20.31 % and urea yield (R urea ) of 606.38 μg mg −1 h −1 . Interestingly, the In doped here not only serves as the active site, but also acts as an activator to stimulate the activity of Bi through electronic interaction, thus making Bi also the active site for the electrocatalytic C-N coupling reaction. Simultaneously, the key intermediates of the reaction are revealed to be *NH 2 and *CO. This work provides further insight into the role of indium in the electrocatalytic C-N coupling for the synthesis of urea, which gives a direction for thinking about the design and construction of subsequent highly efficient electrocatalysts.
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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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）