Journal of the American Chemical Society
·
2017
·
IF 13.858
Shuai Xu,Peng Zhou,Zehui Zhang,Changjun Yang,Bingguang Zhang,Kejian Deng,Steven Bottle,Huaiyong Zhu
Selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is one of the key reactions for producing chemical commodities from biomass and their derivatives. The challenge for this reaction is to develop an efficient catalytic process that can be conducted under mild conditions (room temperature and atmospheric pressure, using oxygen molecules in air as the oxidant) and a recyclable catalyst. Herein we report a photocatalyst of cobalt thioporphyrazine (CoPz) dispersed on g-C3N4 (abbreviated as CoPz/g-C3N4), which exhibits excellent catalytic activity toward the selective oxidation of HMF into FDCA under simulated sunlight using oxygen molecules in air as a benign oxidant. For example, an FDCA yield of 96.1% in an aqueous solution at pH = 9.18 is achieved at ambient temperature and air pressure. At lower pH (4.01), the product generated is 2,5-diformylfuran. Hence, it is possible to control the reaction outcome by control of the pH of the reaction system. g-C3N4 itself is not a suitable catalyst for the selective oxidation because under the experimental conditions g-C3N4 generates hydroxyl radicals that initiate processes that oxidize HMF directly to CO2 and H2O. CoPz on the other hand activates O2 to give singlet oxygen (1O2), which more controllably oxidizes HMF to FDCA albeit at a more moderate yield (36.2%). The strong interaction between the CoPz and g-C3N4 in the CoPz/g-C3N4 catalyst is experimentally evidenced, which not only improves accessibility of the CoPz sites and makes the catalyst recyclable but also disables the hydroxyl radical generation by g-C3N4 and promotes 1O2 generation on the CoPz sites, significantly enhancing the catalytic performance. This study demonstrates the potential for efficient non-noble metal photocatalysts for organic transformations driven by sunlight.
研究领域:
化学工程
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催化科学
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环境科学
✓ 已验证
DOI
高影响因子
Inorganic Chemistry Frontiers
·
2025
·
IF 6.4
Kexin Yang,Zhijia Song,XiaoXiao Fu,Wei Yan,Tao Zhang,Yiwei Hua,Haixin Lin,Qin Kuang,Zhaoxiong Xie
The photocatalytic direct one-step two-electron (2e-) oxygen reduction reaction (ORR) holds great potential in efficient H2O2 synthesis. However, it is still a significant challenge to design photocatalysts for achieving high-efficiency H2O2 production via this direct one-step 2e- ORR pathway. To address this, we have constructed a Z-scheme BAIO/C3N4 heterojunction by in situ growing Ba2AgIO6 (BAIO) on the surface of C3N4 nanosheets. Under visible light irradiation, the optimal sample, with a BAIO:C3N4 mass ratio of 1:1.5, exhibited a remarkable H2O2 yield of up to 535.9 μmol g-1 h-1, which is 8.8 times higher than that of pure C3N4. This enhancement is attributed to the improved charge separation and migration efficiency facilitated by the enhanced internal electric field (IEF) in BAIO/C3N4 heterojunction. Furthermore, the heterojunction altered the O2 adsorption configuration to the Yeager-type, promoting a more efficient and selective direct one-step 2e- ORR for H2O2 production. This study highlights the importance of regulating the reaction pathway to enhance photocatalytic H2O2 production activity and offers a new insight for designing highly active photocatalysts.
研究领域:
光催化
·
材料科学
·
环境科学
·
能量转换
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化学反应工程
✓ 已验证
产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2025
·
IF 9.2
Yongji Xia,Sheng Lin,Jian Yan,Renjie Xu,Yingpeng Du,Chunxiao Song,Dong-Liang Peng,Zhidong Zhou,Jiajia Han,Guanghui Yue
Spinel-type Co3O4 has been identified as a highly prospective cathode catalyst for lithium-oxygen batteries (LOBs), attributable to its distinctive bimetallic active sites that manifest exceptional bifunctional catalytic characteristics. Nonetheless, the practical implementation of this process is constrained by the inherent conductivity limitations of Co3O4 and the suboptimal utilization of active sites. In this study, a Cu-Mn bimetallic doping strategy is employed to prepare a spherical-like structure of Co3O4 formed by self-assembling one-dimensional nanorods. The introduction of Cu²⁺ results in a reduction of the surface energy of the system, thereby facilitating the directional growth of the nanorods. The redox-active Mn³⁺/Mn⁴⁺ pairs exhibit an inhibitory effect on Ostwald ripening, achieved by stabilizing the fine particles during synthesis and regulating solute diffusion kinetics. This combined action of Cu and Mn enhances active site exposure and optimizes charge transfer kinetics. Furthermore, the doping of bimetallic ions resulted in the redistribution of the Co3+/Co2+ ratio, optimizing the electronic structure for efficient charge transfer during the reaction. The combination of tailored electronic states and optimized nanostructures demonstrates excellent dual-functional catalytic activity for ORR and OER, with a half-wave potential of 0.71 V (vs RHE) for OER and an overpotential of 400 mV (10 mA cm-2) for ORR. The assembled LOBs can be stably cycled up to 450 cycles and an ultra-high discharge capacity of 7268 mAh g-1 for LOBs. This study provides a novel reference for the design of efficient bifunctional catalysts.
研究领域:
材料科学
·
电化学
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储能技术
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纳米材料
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催化
✓ 已验证
产品关联
DOI
高影响因子
RESEARCH ON CHEMICAL INTERMEDIATES
·
2025
·
IF 3.5
Yan Jiaqi,Chen Wenkai,Ni Wenjin,Li Lu,Fu Jinfeng,Yang Qian,Yang Zhiyong
N -cyclohexylcyclohexanimine (N-CCA), a by-product of cyclohexylamine (CHA) oxidation to cyclohexanone oxime (CHO), was used as the starting reactant for the efficient conversion to CHO under an oxygen atmosphere, utilizing the constructed surface hydroxyl-rich Ti-based catalysts. Of these, the 20% TiO 2 /Hβ catalyst exhibited unique catalytic activity and stability, achieving 45.9% N-CCA conversion and 82.1% CHO selectivity, with the content of high-boiling by-products not exceeding 1.0%. The superior catalytic performance, as evidenced by characterization results, stems primarily from: (i) the combination of TiO 2 and Hβ, which promotes the formation of a high specific surface area with fine TiO 2 nanoparticles and high-density Ti δ+ active sites, which facilitate the adsorption and activation of N-CCA; (ii) the construction of rich hydroxyl groups, which enhances the Brønsted acid sites, thereby improving the generation of active oxygen species; (iii) the intercrystalline embedding of TiO 2 and Hβ, which forms Ti–O–Si bonds, effectively inhibiting Ti leaching and ensuring excellent catalyst stability. The conversion of N-CCA, the main by-product of CHA oxidation, to the desired CHO using an efficient and robust 20% TiO 2 /Hβ catalyst represents an attractive pathway.
研究领域:
催化
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材料科学
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化学反应工程
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表面化学
✓ 已验证
产品关联
DOI
高影响因子
NEW CARBON MATERIALS
·
2025
·
IF 6.8
Xiu-zhen LV,Xiang-xiang XU,Meng-meng YU,Yi-chen WEI,Jun-ying WANG,Jun-zhong WANG
The need for bi-functional catalysts that facilitate both the oxygen reduction (ORR) and carbon dioxide reduction (CO 2 RR) reactions arises from their potential to help solve the critical problems of carbon neutrality and renewable energy conversion. However, there are few reports on the development of bi-functional catalysts for zinc-air battery-driven CO 2 RR devices. We introduce a novel approach for synthesizing Fe 2 N/Fe 3 C species embedded in nitrogen-doped carbon nanofibers by electrospinning a solution of Hemin and polyacrylonitrile in N,N-dimethylformamide. The material has an exceptional catalytic performance, with a half-wave potential of 0.91 V versus RHE for the ORR and values of over 90% for both the selectivity and Faradaic efficiency for the CO 2 RR. The high catalytic performances are attributed to the strong coupling between the Fe 3 C/Fe 2 N heterostructure and the Fe-N-C sites in the nitrogen-doped carbon nanofibers. Notably, both Fe 3 C and Fe 2 N play distinct roles in both the ORR and CO 2 RR. This investigation indicates a way for designing advanced carbon-based bi-functional catalysts for use in this field.
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研究领域:
材料科学
·
电化学
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL PHYSICS LETTERS
·
2017
·
IF 1.815
W.S. Huo,H. Zeng,Y. Yang,Y.H. Zhang
Enzymatic electrodes over-coated by thin film of nano-composite made up of polymer and functionalized nano-gold particle was prepared. Glucose/O 2 membrane-free enzymatic fuel cell based on nano-composite based electrodes with incorporated glucose oxidase and laccase was assembled. This enzymatic fuel cell exhibited high energy out-put density even when applied in human serum. Catalytic cycle involved in enzymatic fuel cell was limited by oxidation of glucose occurred on bioanode resulting from impact of sophisticated interaction between active site in glucose oxidase and nano-gold particle on configuration of redox center of enzyme molecule which crippled catalytic efficiency of redox protein.
研究领域:
生物化学
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纳米生物学
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能源科学
✓ 已验证
DOI
高影响因子
Batteries-Basel
·
2023
·Vol. 9
·期 5
·
IF 4
Ningning Feng,Chaoqiang Wang,Jing Wang,Yang Lin,Gang Yang
Lithium–oxygen (Li-O2) batteries have captured worldwide attention owing to their highest theoretical specific energy density. However, this promising system still suffers from huge discharge/charge overpotentials and poor cycling stability, which are related to the leakage/volatilization of organic liquid electrolytes and the inefficiency of solid catalysts. A mixing ionic liquid-based gel polymer electrolyte (IL-GPE)-based Li-O2battery, consisting of a 20 mM 2,5-di-tert-butyl-1,4-benzoquinone (DBBQ) 40 mM N-methylphenothiazine (MPT)-containing IL-GPE and a single-walled carbon nanotube cathode, is designed for the first time here. This unique dual redox mediators-based GPE, which contains a polymer matrix immersed with mixed ionic liquid electrolyte, provides a proper ionic conductivity (0.48 mS cm−1) and effective protection for lithium anode. In addition, DBBQ, as the catalyst for an oxygen reduction reaction, can support the growth of discharge products through the solution–phase pathway. Simultaneously, MPT, as the catalyst for an oxygen evolution reaction, can decompose Li2O2at low charge overpotentials. Hence, the DBBQ-MPT-IL-GPE-based Li-O2battery can operate for 100 cycles with lower charge/discharge overpotentials. This investigation may offer a promising method to realize high-efficiency Li-O2/air batteries.
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2019
·
IF 8.456
Yuan Meng,Jianguo Jiang,Aikelaimu Aihemaiti,Tongyao Ju,Yuchen Gao,Jiwei Liu,Siyu Han
Amine-functionalized sorbents are investigated widely for CO2 capture from flue gas, to mitigate the crisis of global CO2 emission, with the advantages of excellent adsorption and regeneration performance. However, the presence of O2 in flue gas (3–10%) would induce the degradation of the sorbents, and some previous works proposed the strategies at the sacrifice of partial CO2 adsorption capacity. Herein, we focused on the oxidation behavior of PEI-functionalized silica in the long-term operation and analyzed the degradation mechanism by characterizing the oxidized sorbents. The sorbent proved to be oxidative stable under a lower temperature of air exposure, but the oxidative degradation would indeed occur at more harsh temperatures (above 90 °C). This study demonstrated that CO2 capture from O2-containing flue gas was feasible by controlling the operating temperature (below 75 °C), and the effective capacity of above 135 mg/g could be maintained in the cyclic CO2 capture.
研究领域:
环境科学
·
化学工程
·
碳捕集与封存（CCS）
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材料科学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2018
·
IF 8.097
Qiong Yang,Peng-Fei Wang,Jin-Zhi Guo,Zi-Ming Chen,Wei-Lin Pang,Ke-Cheng Huang,Yu-Guo Guo,Xing-Long Wu,Jing-Ping Zhang
As a promising cathode material of sodium-ion battery, P2-type Na2/3Ni1/3Mn2/3O2 (NNMO) possesses a theoretically high capacity and working voltage to realize high energy storage density. However, it still suffers from poor cycling stability mainly incurred by the undesirable P2–O2 phase transition. Herein, the electrochemically active Fe3+ ions are introduced into the lattice of NNMO, forming Na2/3Ni1/3Mn2/3–xFexO2 (x = 0, 1/24, 1/12, 1/8, 1/6) to effectively stabilize the P2-type crystalline structure. In such Fe-substituted materials, both Ni2+/Ni4+ and Fe3+/Fe4+ couples take part in the redox reactions, and the P2–O2 phase transition is well restrained during cycling, as verified by ex situ X-ray diffraction. As a result, the optimized Na2/3Ni1/3Mn7/12Fe1/12O2 (1/12-NNMF) has a long-term cycling stability with the fading rate of 0.05% per cycle over 300 cycles at 5 C. Furthermore, the 1/12-NNMF delivers excellent rate capabilities (65 mA h g–1 at 25 C) and superior low-temperature performance (the capacity retention of 94% at −25 °C after 80 cycles) owing to the enhanced Na diffusion upon Fe doping, which is deduced by the studies of electrode kinetics. More significantly, the 1/12-NNMF also displays remarkable sodium-ion full-cell properties when merged with an LS–Sb@G anode, thus implying the possibility of their practical application.
研究领域:
材料科学
·
电化学
·
能量存储
·
电池技术
✓ 已验证
DOI
高影响因子
Catalysis Science & Technology
·
2025
·
IF 4.2
Yu-Le Wang,Songhai Wu,Yu-Zhen Xu,Yu-Dong Shan,Yong Liu,Xu Han
The selective oxidation of cyclohexene (Cy) to cyclohexene oxide (Cy-ep) using O2 remains challenging due to low epoxidation selectivity. In this work, a series of Mo-doped TS-1 (Mo-TS-1) catalysts were successfully synthesized for the epoxidation of Cy under solvent- and initiator-free conditions with O2 as the oxidant. Among them, 5Mo-TS-1 exhibited high catalytic performance, achieving 43.5% Cy conversion and 50.6% selectivity toward Cy-ep. Additionally, valuable byproducts such as 2-cyclohexen-1-ol (Cy-ol) and 2-cyclohexen-1-one (Cy-one) were obtained with yields of 28.0% and 21.4%, respectively. Since both Cy-ol and Cy-one are valuable intermediates in fragrance synthesis, over 43.5% of Cy was effectively converted into high-value products. Quenching experiments and Raman spectroscopy revealed that surface oxygen vacancies (Ov) facilitate the activation of O2 to form ≡Ov‑superoxo species, which abstract hydrogen from the allylic C-H bond of Cy to generate 3-cyclohexenyl radicals (Cy•). These radicals subsequently react with O2 to form Cy-OO•, followed by hydrogen abstraction from another Cy molecule to yield 2-cyclohexene-1-hydroperoxide (Cy-OOH). A positive correlation between Cy-OOH and Cy-ep formation underscores the critical role of Cy-OOH in the epoxidation process. Furthermore, Raman spectroscopy confirmed the presence of ≡Mo-(η2-O2) peroxo species on the catalyst surface, which preferentially attack the C=C bond of Cy to form Cy-ep. DFT calculations elucidated two distinct O2 activation pathways: In Pathway I, O2 is activated at Ov sites to form ≡Ov‑superoxo, which subsequently reacts with Cy to generate ≡Ov‑peroxo, Cy-OOH, and Cy•. In Pathway II, Mo(V/VI) sites either directly activate O2 or react with peroxo intermediates (≡Ov‑peroxo or Cy-OOH) to form ≡Mo-(η2-O2). This species selectively epoxidizes the alkene bond in Cy to Cy-ep. Notably, the direct activation of O2 at Mo(V/VI) sites bypasses the allylic oxidation route, thereby enhancing the epoxidation selectivity beyond the theoretical limit of 50.0%. This study provides new insight on the importance of surface superoxo and peroxo mediated by Ov and Mo(V/VI) in the epoxidation processes.
研究领域:
催化化学
·
材料化学
·
绿色化学
·
多相催化
·
氧化反应
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2017
·Vol. 27
·期 43
·1700626
·
IF 12.124
Chi Zhang,Wei-Hai Chen,Li-Han Liu,Wen-Xiu Qiu,Wu-Yang Yu,Xian-Zheng Zhang
Conventional photodynamic therapy (PDT) has limited applications in clinical cancer therapy due to the insufficient O 2 supply, inefficient reactive oxygen species (ROS) generation, and low penetration depth of light. In this work, a multifunctional nanoplatform, upconversion nanoparticles (UCNPs)@TiO 2 @MnO 2 core/shell/sheet nanocomposites (UTMs), is designed and constructed to overcome these drawbacks by generating O 2 in situ, amplifying the content of singlet oxygen ( 1 O 2 ) and hydroxyl radical (•OH) via water-splitting, and utilizing 980 nm near-infrared (NIR) light to increase penetration depth. Once UTMs are accumulated at tumor site, intracellular H 2 O 2 is catalyzed by MnO 2 nanosheets to generate O 2 for improving oxygen-dependent PDT. Simultaneously, with the decomposition of MnO 2 nanosheets and 980 nm NIR irradiation, UCNPs can efficiently convert NIR to ultraviolet light to activate TiO 2 and generate toxic ROS for deep tumor therapy. In addition, UCNPs and decomposed Mn 2+ can be used for further upconversion luminescence and magnetic resonance imaging in tumor site. Both in vitro and in vivo experiments demonstrate that this nanoplatform can significantly improve PDT efficiency with tumor imaging capability, which will find great potential in the fight against tumor.
研究领域:
癌症治疗
·
纳米技术
·
生物医学工程
·
光化学
·
成像技术
✓ 已验证
DOI
高影响因子
BIOORGANIC CHEMISTRY
·
2023
·
IF 5.1
Xinxin Liu,Lei Chen,Ze Chen
Photodynamic therapy (PDT) has emerged as a highly efficacious therapeutic modality for malignant tumors owing to its non-invasive property and minimal adverse effects. However, the pervasive hypoxic microenvironment within tumors significantly compromises the efficacy of oxygen-dependent PDT, posing a formidable challenge to the advancement of high-efficiency PDT. Here, we developed a nanostructured photosensitizer (PS) assembled by cationic and anionic zinc phthalocyanines to load oxygen-throttling drug atovaquone (ATO), which was subsequently coated with polydopamine to obtain the final product ATO/ZnPc-CA@DA. ATO/ZnPc-CA@DA exhibited excellent stability, particularly in the blood milieu. Interestingly, the acidic microenvironment can trigger drug release from ATO/ZnPc-CA@DA, leading to a significant enhancement in fluorescence and an augmented generation of reactive oxygen species (ROS). ATO/ZnPc-CA@DA can induce synergistic cytotoxicity of PS and ATO, and significantly enhance the killing ability against tumor cells under hypoxic conditions. The mechanism underlying cytotoxicity of ATO/ZnPc-CA@DA was demonstrated to be associated with augmented cell apoptosis, disruption of mitochondrial membrane potential, diminished ATP production, heightened intracellular ROS generation, and reduced intracellular oxygen consumption. The animal experiments indicated that ATO/ZnPc-CA@DA possessed enhanced tumor targeting capability, along with a reduction in PS distribution within normal organs. Furthermore, ATO/ZnPc-CA@DA exhibited enhanced inhibitory effect on tumor growth and caused aggravated damage to tumor tissue. The construction strategy of nanostructured PS and the synergistic antitumor principle of combined oxygen-throttling drugs can be applied to other PSs, thereby advancing the development of photodynamic antitumor therapy and promoting the clinical translation.
研究领域:
生物医学工程
·
肿瘤学
·
药剂学
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）