CHINESE JOURNAL OF CATALYSIS
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2017
·
IF 2.813
Yi Liu,Xuanmu Zhou,Zhehui Zhang,Bingguang Zhang,Kejian Deng
The photocatalytic activity of cobalt octakis(butylthio) porphyrazine (CoPz(BuS) 8 ) was assessed through photodegradation of the dye rhodamine B (RhB) in water under irradiation with a Xe lamp and aerated conditions. The photocatalytic activity of CoPz(BuS) 8 loaded on Al 2 O 3 or SiO 2 @Fe 3 O 4 nanoparticles or coordinated with an axial azide ligand was also investigated. The results demonstrated that the photocatalytic activity of CoPz(BuS) 8 loaded on Al 2 O 3 was higher than that loaded on SiO 2 @Fe 3 O 4 . The kinetic curves of RhB degradation in aqueous solutions at different pH indicated the pseudo first-order kinetics of the reaction. The highest degradation rate for CoPz(BuS) 8 loaded Al 2 O 3 at pH = 4 after 160 min was 84.6%. However, the advantages of easier separation and recycling as well as the ability to terminate the reaction at any time for the CoPz(BuS) 8 loaded SiO 2 @Fe 3 O 4 cannot be ignored. When electron-rich NaN 3 was coordinated with CoPz(BuS) 8 as an axial ligand and loaded on Al 2 O 3 , the resulting catalyst produced more active oxygen species such as O 2 − and HO • to promote the quicker degradation of RhB than that by the other catalysts. For the N 3 -coordinated CoPz(BuS) 8 loaded on Al 2 O 3 , the reactions at pH = 4 and 7 distinctly deviated from first-order kinetics, and the degradation rate reached 77.6% after 80 min at pH = 4.
研究领域:
化学
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环境科学
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材料科学
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产品关联
DOI
高影响因子
TRANSACTIONS OF TIANJIN UNIVERSITY
·
2021
·Vol. 28
·期 1
·73-79
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IF 0
Tian Pengfei,Su Jianjun,Song Yun,Ye Ruquan,Zhu Minghui
Great attention has been paid to cofacial porphyrins due to their many unique advantages over their monomeric analogs. However, their synthesis is usually complicated. In this work, a facile impregnation method for preparing heterogenized, cofacially stacked porphyrins is proposed. An anionic porphyrin is introduced as an underlayer for immobilization of cationic cobalt porphyrin via electrostatic force. The metal center of the underlying molecule contributes to the electronic structure of the upper cationic cobalt porphyrin. Screening reveals the anionic iron porphyrin to be the most efficient underlayer molecule, lowering the activation energy barrier of CO 2 electroreduction, with an improved turnover frequency by 74% to 8.0 s −1 at − 0.6 V versus RHE.
研究领域:
化学
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材料科学
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催化
✓ 已验证
DOI
APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
·
IF 20.2
Yuanyuan Qi,Shuming Li,Tengfei Bao,Ping She,Heng Rao,Jun-sheng Qin
Molecular catalysts have attracted significant attention in photocatalytic CO 2 reduction (PCR) due to well-defined structure and exceptional catalytic selectivity. However, they are still limited by recycling challenges and inherent instability. Forming an organic-inorganic composite can address these issues and enhance PCR performance simultaneously. Herein, we developed a flower-like Z-scheme heterojunction of cobalt porphyrin ([meso-tetra(4-sulfonatophenyl)porphyrin], CoTPPS) and ZnIn 2 S 4 (ZIS). The optimized ZIS@CoTPPS exhibited a superior CO evolution rate of 388.26 μmol g −1 h −1 , which is 8.96 times of pristine ZIS (43.32 μmol g −1 h −1 ). The superior PCR activity is contributed by the enhanced light absorption, and photoinduced charge separation facilitated by the Z-scheme structure and the cobalt active sites. Moreover, theoretical calculations confirm the heterojunction relies on a substantial interfacial coupling between the Zn atoms of ZIS and the sulfonic acid groups of CoTPPS through coordination assembly. This investigation affords a useful inspiration for consciously constructing novel ZIS-incorporated atomistic Z-scheme photocatalysts.
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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产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2024
·
IF 8.1
Ziyi Wang,Yuqin Wei,Zhaoli Xue,Lei Feng,Aijian Wang,Yan Sun,Chunsheng Li,Xinping Qiu,Long Zhao
Asymmetric metalloporphyrins are potential electrocatalysts to construct composites for efficient oxygen reduction reactions (ORRs) due to their inherent large dipole moment , which facilitates the charge separation. To find more effective molecular structures towards the ORRs, in particular their performance and electrolyte relationship, we rationally designed two A3B-type asymmetric cobalt porphyrin aPh-TCoP and aBA-TCoP with phenyl and benzoic acid as substituents, respectively. The ORR performance of the porphyrin-decorated carbon black composites was examined in five electrolytes at different pH values spanning from 0.7 to 13.7. It was found that aBA-TCoP/C exhibited better ORR activity and selectivity than aPh-TCoP/C in all solutions. Interestingly, both composites demonstrated their highest ORR activity in the pH13.7 electrolyte and exhibited 4-electron selectivity in the pH3.7 solution. This conclusion is drawn from a comprehensive analysis of various electrochemical properties , encompassing current density , reduction potentials, electron transfer numbers, and intermediate yields. The results illustrate the regulation of ORR properties by altering the electrolyte pH and a notable improvement in the ORR performance through the modification of porphyrin substituents. These findings offer a foundational understanding for the design of efficient metalloporphyrins and the attainment of controlled oxygen reduction in electrochemical devices .
研究领域:
电化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF SOLID STATE ELECTROCHEMISTRY
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2014
·Vol. 19
·期 2
·497-506
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IF 2.234
Jiang Liqing,Cui Lili,He Xingquan
Cobalt 5,10,15,20-tetrakis(4-pyridyl)porphyrin (CoTPyP) micro/nanoparticles assembled on poly(sodium-p-styrenesulfonate) (PSS) modified reduced graphene oxide (PSS-rGO) as a nonnoble catalyst for oxygen reduction reaction (ORR) was prepared by an in situ solvothermal synthesis method. The CoTPyP/PSS-rGO micro/nanocomposite was characterized by UV-vis spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscope (SEM) techniques. Cyclic voltammetry (CV) measurement result disclosed that CoTPyP/PSS-rGO possesses quite high electrochemically accessible surface area, which was more than tripled as large as the bare glassy carbon (GC) electrode. Rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) techniques were employed to study the catalytic activity and the ORR mechanism of as-synthesized CoTPyP/PSS-rGO catalyst in an alkaline medium. Linear sweep voltammetry (LSV) tests showed that the half-wave potential for ORR on the CoTPyP/PSS-rGO catalyst was found to be around −0.22 V vs. saturated calomel electrode (SCE), which was similar to that on Pt/C (−0.20 V vs. SCE). RRDE results displayed that the percentage of hydrogen peroxide yielded on the CoTPyP/PSS-rGO composite was less than 20 %, and the ORR process mainly proceeded via an almost direct 4-electron pathway. Moreover, the assembled CoTPyP/PSS-rGO catalyst possessed good stability and excellent tolerance to the crossover effect of methanol for ORR.
研究领域:
电化学
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纳米材料
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能源材料
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催化化学
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表面科学
✓ 已验证
DOI
高影响因子
MICROCHEMICAL JOURNAL
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2024
·
IF 4.9
Yicheng Zhou,Rongrong Qiao,Li Dong,Jiazheng Zhang,Lin Liu,Chao Liu,Xiaobo Zhang,Zhiwei Tong
A nanocomposite of 5,10,15,20-tetrakis (N-methylpyridinium-4-yl) porphyrin cobalt (III) (CoTMPyP) and titanium oxide (Ti 4 O 9 2− ) nanosheets was constructed using a stripping/self-assembly method for the first time. The morphology, structure, and composition of CoTMPyP/Ti 4 O 9 2− were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Electrochemical impedance spectroscopy (EIS), Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques were utilized to analyze the electrochemical properties and detect uric acid (UA), guanine (G), and adenine (A). Under optimized conditions (0.1 M phosphate buffer, pH 4.0), the CoTMPyP/Ti 4 O 9 2− modified glassy carbon electrode (GCE) enabled simultaneous detection of UA, G, and A with detection limits of 396, 59, and 47 nM, respectively (S/N = 3). The linear detection ranges were 0.31–16.99 μM for UA, and 0.12–4.02 μM for both G and A. The stability and anti-interference ability of the CoTMPyP/Ti 4 O 9 2− /GCE sensor were also examined. Further tests in serum samples demonstrated recoveries of 98.1–109.7 % for the biomolecules, with relative standard deviations of 0.8–6.2 %. These results indicate excellent performance of the nanocomposite sensor for electrochemical detection.
研究领域:
分析化学
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生物医学工程
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
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2012
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IF 1.171
Xiantai ZHOU,Hongbing JI
The highly efficient aerobic oxidation of alcohols to carbonyl compounds was achieved catalyzed by cationic meso -tetrakis (1-methyl-4-pyridyl, TM4PyP) metalloporphyrins immobilized in montmorillonite interlayers. Cobalt porphyrin (CoTM4PyP-MT) showed excellent activity and selectivity in the aerobic oxidation of benzyl alcohol, where 90% yield of benzaldehyde was obtained. CoTM4PyP-MT can be five times reused without significant loss of activity. 摘要 制备了蒙脱土负载的离子型四 (1-甲基-4-吡啶基) 金属卟啉, 并用于催化醇类氧化制备羰基化合物的反应中. 结果表明, 该催化剂表现出优异的活性和产物选择性, 其中在苯甲醇氧化反应中, 苯甲醛收率可达 90%, 且连续重复使用 5 次后, 其活性未见明显下降.
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
CHINESE JOURNAL OF STRUCTURAL CHEMISTRY
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2022
·
IF 0.847
Wei-Feng YOU,Xiao XU,Ai-Hui CAO,Zhi-Jie TAO,Long-Tian KANG
The electrocatalysts containing cobalt-pyrrolic nitrogen-carbon (Co-N 4 -C) moiety for CO 2 reduction reaction (CO 2 RR) have caught much attention. However, the effects of Co valence state and its synergy with graphene substrate are not clear yet. In this work, cobalt porphyrin (CoTPP) molecule with the intrinsic Co-N 4 -C moiety is successfully combined with graphene oxide (GO) via three kinds of liquid-phase methods. The ratio of CoTPP to GO and the valence state of Co atom are studied to explore their catalysis for CO 2 RR to CO. It is found that axially-coordinated Co(III)TPPCl/GO nanocomposites synthesized via a chemical method exhibit better ability for CO 2 RR, as compared with Co(II)TPP+GO and/or Co(III)TPPCl+GO nanocomposites obtained via a physically mixing way. After optimizing the ratio of CoTPP to GO, the Faradaic efficiency (FE) is more than 90% for CO 2 RR to CO between –0.7 and –0.8 V vs . reversible hydrogen electrode (RHE) in Co(III)TPPCl/GO75. The synergy between CoTPP and GO and the effect of Co valence state are systematically investigated, indicating that their strong interaction plays the key role in electrocatalytic CO 2 RR.
研究领域:
材料科学
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电化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2015
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IF 4.321
Langchang Gao,Kejian Deng,Judun Zheng,Bing Liu,Zehui Zhang
In this study, a new method was developed for the oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) over Merrifield resin supported Co(II)–meso-tetra(4-pyridyl)-porphyrin (abbreviated as Merrifield resin-Co-Py). Diffuse reflectance spectra showed that Co(II)–meso-tetra(4-pyridyl)-porphyrin was successfully bonded on the Merrifield resin. The Merrifield resin-Co-Py catalyst was used for the oxidation of HMF into FDCA, and several parameters were studied. Tert-butyl hydroperoxide was the best oxidant among other common oxidants. The reaction solvent greatly affected both HMF conversion and product selectivity. High HMF conversion of 95.6% and FDCA yield of 90.4% were obtained at 100 °C after 24 h. Time course of HMF conversion over Merrifield resin-Co-Py showed that 2,5-diformylfuran was the intermediate for the conversion of HMF into FDCA. The catalyst could be reused without the significant loss of its catalytic activity.
研究领域:
化学工程
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生物质转化
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催化化学
✓ 已验证
DOI
高影响因子
ChemSusChem
·
2022
·Vol. 15
·期 8
·e202200090
·
IF 9.14
Wenwen Bao,Senhe Huang,Diana Tranca,Boxu Feng,Feng Qiu,Fermín Rodríguez-Hernández,Changchun Ke,Sheng Han,Xiaodong Zhuang
Graphical Beauty in balanced asymmetry : An asymmetric Co II porphyrin ( as -PorCo) is constructed with a substituent of 2,6-dimethylbenzene to enhance the charge transfer capability from carbon nanotubes to as -PorCo, resulting in large partial current density of 8 mA cm −2 and high turnover frequency of 5656 h −1 at −0.7 V vs. reversible hydrogen electrode in aqueous solution. The present study provides the new insight into molecular design of catalysts for efficient electrochemical CO 2 reduction. The electrochemical reduction of carbon dioxide (CO 2 ) based on molecular catalysts has attracted more attention, owing to their well-defined active sites and rational structural design. Metal porphyrins (PorMs) have the extended π-conjugated backbone with different transition metals, endowing them with unique CO 2 reduction properties. However, few works focus on the investigation of symmetric architecture of PorMs as well as their aggregation behavior to CO 2 reduction. In this work, a series of Co II porphyrins (PorCos) with symmetric and asymmetric substituents were used as model of molecular catalysts for CO 2 reduction. Owing to the electron donating effect of 2,6-dimethylbenzene (DMB), bandgaps of the complexes became narrower with the increasing number of DMB. As electrocatalysts, all PorCos exhibited promising electrocatalytic CO 2 reduction performance. Among the three molecules, asymmetric Co II porphyrin ( as -PorCo) showed the lowest onset potential of −288 mV and faradaic efficiencies exceeding 93 % at −0.6 V vs. reversible hydrogen electrode, which is highly competitive among the reported state-of-art porphyrin-based electrocatalysts. The CO 2 reduction performance depended on π-π stacking between PorCo with carbon nanotubes (CNTs) and adjacent PorCos, which could be readily controlled by atomically positioned DMB in PorCo. Density functional theory calculations also suggested that the charge density between PorCo and CNT was highest due to the weak steric hindrance in as -PorCo, providing the new insight into molecular design of catalysts for efficient electrochemical CO 2 reduction.
研究领域:
催化化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nano Research
·
2020
·Vol. 13
·期 10
·2665-2672
·
IF 8.183
Tian Shufang,Chen Sudi,Ren Xitong,Hu Yaoqing,Hu Haiyan,Sun Jiajie,Bai Feng
Nanoparticle photosensitizers possess technical advantages for photocatalytic reactions due to enhanced light harvesting and efficient charge transport. Here we report synthesis of semiconductor nanoparticles through covalent coupling and assembly of metalloporphyrin with condensed carbon nitride. The resultant nanoparticles consist of light harvesting component from the condensed carbon nitride and photocatalytic sites from the metalloporphyrins. This synergetic particle system effectively initiates efficient charge separation and transport and exhibits excellent photocatalytic activity for CO 2 reduction. The CO production rate can reach up to 57 µmol/(gh) with a selectivity of 79% over competing H 2 evolution. Controlled experiments demonstrate that the combination of light harvesting with photocatalytic activity via covalent assembly is crucial for the high photocatalytic activity. Due to effective charge separation and transfer, the resultant nanoparticle photocatalysts show exceptional photo stability against photo-corrosion under light irradiation, enabling for long-term utilization. This research opens a new way for the development of stable, effective nanoparticle photocatalysts using naturally abundant porphyrin pigments.
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
产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2021
·
IF 6.901
Xuanhe Hu,Tian Huang,Shipeng Wang,Shangjun Lin,Zihao Feng,Lai-Hon Chung,Jun He
The shuttle effect of soluble polysulfides as one of the primary bottlenecks has retard the widespread use of lithium-sulfur (Li-S) batteries. In this work, a new functional separator coating composed of pristine zirconium metal-organic framework (Co-PCN-222) with catalytic cobalt-porphyrin linker decorated carbon nanotubes (PCN@CNT) was presented for addressing this problem. Benefiting from powerful adsorption and catalytic activity of the uniformly dispersed cobalt and nitrogen sites in porphyrin linkers as well as the fast electron transport network provided by highly conductive CNT, the polysulfide redox kinetics is greatly boosted and the shuttle effect is inhibited to a large extent. Accordingly, the Li-S batteries coupling with PCN@CNT coated separator delivers a specific capacity as high as 1157 mAh g −1 at 0.1 C, good rate capability with a reversible capacity of 696 mAh g −1 under 2 C as well as excellent cyclic performance with a low average capacity attenuation rate of 0.067% upon 500 cycles at 1 C. This work will open up great opportunities in the development of pristine MOFs-based separator coating for advanced Li-S batteries.
研究领域:
材料科学
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电化学
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能源存储技术
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）