Journal of Materials Chemistry C
·
2020
·Vol. 9
·期 5
·1593-1603
·
IF 7.059
Guoming Gao,Ximeng Wang,Qifeng Chen,Caibo Xie,Jie Zheng,Huailin Fan,Lulu Ma,Ruifang Guan,Yanfen Fang,Xun Hu
Surface fluorinated TiO2 has received extensive attention in recent years due to the improved photocatalytic reactivity compared with that of pure TiO2. However, the synergy of surface fluorine (FS) and oxygen vacancy (VO) is not clear and needs further study. Here we systematically studied the effect of FS, VO and acidic sites of TiO2 nanosheets on the selective photocatalytic oxidation of benzylamine to imine. The photocatalytic activity first increased and then decreased as the content of FS decreased and VO increased. The photocatalytic activity reached a summit with the imine yield of 92.1% over TiO2-B-6 h, which is mainly due to the synergy between FS and adjacent VO, forming the frustrated Lewis pair that boosts the activation of O2. The varied contents of FS and VO not only cause an evident change in the amount of acidic sites, but also affect the band structure and separation efficiency of charge carriers. The experimental and calculation results demonstrate that the coexistence of FS and VO boosted the separation efficiency, density and mobility of photogenerated charge carriers, resulting in the improved photocatalytic activity. The improved photocatalytic activity can be attributed to the combined effects of FS, VO and acidic sites. This work provides a strategy for the explicit regulation of surface species on TiO2 nanosheets for improved photocatalytic activity.
研究领域:
材料科学
·
环境科学
·
化学工程
✓ 已验证
DOI
高影响因子
Catalysts
·
2025
·Vol. 15
·期 7
·694
·
IF 4
Ziyan Mi,Huayun Long,Yuhua Jia,Yue Ma,Cuilan Miao,Yan Xie,Xiaomei Zhu,Jiahui Huang
The development of non-noble metal catalysts for gas-phase propylene epoxidation with H2/O2remains challenging due to their inadequate activity and stability. Herein, we report a Cs+-modified Ni/TS-1 catalyst (9%Ni-Cs/TS-1), which exhibits unprecedented catalytic performance, giving a state-of-the-art PO formation rate of 382.9 gPO·kgcat−1·h−1with 87.8% selectivity at 200 °C. The catalyst stability was sustainable for 150 h, far surpassing reported Ni-based catalysts. Ni/TS-1 exhibited low catalytic activity. However, the Cs modification significantly enhanced the performance of Ni/TS-1. Furthermore, the intrinsic reason for the enhanced performance was elucidated by multiple techniques such as XPS, N2physisorption, TEM,29Si NMR, NH3-TPD-MS, UV–vis, and so on. The findings indicated that the incorporation of Cs+markedly boosted the reduction of Ni, enhanced Ni0formation, strengthened Ni-Ti interactions, reduced acid sites to inhibit PO isomerization, improved the dispersion of Ni nanoparticles, reduced particle size, and improved the hydrophobicity of Ni/TS-1 to facilitate propylene adsorption/PO desorption. The 9%Ni-Cs/TS-1 catalyst demonstrated exceptional performance characterized by a low cost, high activity, and long-term stability, offering a viable alternative to Au-based systems.
研究领域:
催化化学
·
化学工程
·
材料科学
·
多相催化
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2025
·
IF 9.5
Guangqi Zhang,Congcong Dang,Yiping Liu,Rouyan Guo,Lingti Kong,Liancheng Zhao,liming Gao
Li-O2 batteries have emerged as promising contenders for advanced energy storage systems, leveraging their exceptionally high theoretical energy density. Nevertheless, their practical deployment is substantially hindered by rapid capacity degradation and restricted operational durability, primarily attributed to sluggish oxygen reaction kinetics. Here, to modulate kinetic barriers, we propose an approach synergizing structural and electronic advantages by integrating heterointerface engineering and hierarchical nano structuring. A hollow nanobox MoSe2@CuS core-shell heterostructure is developed as a bifunctional oxygen electrode. Such heterostructure could induce a built-in electric field to modulate charge transfer dynamics and the hollow architecture could optimize triple-phase interfacial reactions. Leveraging the synergistic attributes of its components, the MoSe2@CuS-based Li-O2 battery achieves an excellent specific capacity of 16,000 mAh g-1 at 100 mA g-1. Moreover, it demonstrates remarkable cycling durability, sustaining high performance for over 190 cycles at 200 mA g-1 with a restricted capacity of 600 mAh g-1. Density functional theory (DFT) calculations further illustrate the lowered energy kinetic barrier for Li2O2 formation/decomposition induced by MoSe2@CuS core-shell heterostructure. This work pioneers a universal heterointerface engineering strategy through rational design of hierarchical hollow architectures, providing new insights for developing high-performance Li-O2 battery cathodes.
研究领域:
储能
·
纳米材料
·
电化学
·
电池技术
·
材料科学
·
理论化学
✓ 已验证
DOI
高影响因子
Materials Today Communications
·
2025
·
IF 4.5
Jiaqi Wang,Xiqiang Huang,Xingbao Zhu,Yuanguo Wu,Zining Man,Xiangyu Wen,Weiting Qi,Xing Tang,Zhe Lü
Despite their potential to enhance safety and design flexibility in next-generation lithium batteries, particularly lithium-oxygen (Li-O 2 ) systems, solid polymer electrolytes (SPEs) face persistent challenges of insufficient ionic conductivity and high interfacial resistance. To address these limitations, we developed a novel PEGDA-based quasi-solid-state electrolytes (QSEs) through in situ polymerization, strategically incorporating three functional additives: cellulose acetate (CA), N-methyl-2-pyrrolidone (NMP), and fluoroethylene carbonate (FEC). The electrolyte design leverages multiple synergistic mechanisms: hydrogen bonding between CA and NMP optimizes microstructural organization for efficient Li⁺ transport pathways; carbonyl groups in NMP coordinate with Li⁺ to facilitate LiTFSI dissociation, while oxygen-rich functional groups in CA provide supplementary Li⁺ coordination sites; FEC is introduced to further improve interfacial stability. This molecular engineering approach achieves an impressive room-temperature ionic conductivity of 8.54 × 10 −4 S cm −1 and a high lithium-ion transference number of 0.78. The QSE demonstrated excellent cycling stability (>900 h) in lithium symmetrical batteries and significantly improved the discharge capacity (12243 mAh g −1 ) and long-term cycling performance (590 h) of Li-O 2 batteries. These results highlight the efficacy of our multi-functional additive strategy in overcoming fundamental limitations in solid electrolytes, offering important insights for the rational design of high-performance energy storage systems.
研究领域:
储能
·
材料科学
·
电化学
·
聚合物电解质
·
电池技术
✓ 已验证
产品关联
DOI
高影响因子
Chem
·
2019
·
IF 18.205
Rongan Shen,Wenxing Chen,Qing Peng,Siqi Lu,Lirong Zheng,Xing Cao,Yu Wang,Wei Zhu,Juntao Zhang,Zhongbin Zhuang,Chen Chen,Dingsheng Wang,Yadong Li
Summary The electrochemical direct synthesis of hydrogen peroxide (H 2 O 2 ) is significant but still challenging because of the lack of highly selective and active catalysts. Here, we report the synthesis of hollow nanospheres constructed by atomically dispersing platinum in amorphous CuS x support (h-Pt 1 -CuS x ) with a high concentration of single atomic Pt sites (24.8 at%), and this catalyst can consistently reduce O 2 into H 2 O 2 with selectivity of 92%–96% over a wide potential range of 0.05–0.7 V versus RHE in HClO 4 electrolyte. Scanning transmission electron microscopy and X-ray absorption fine structure spectroscopy confirmed the atomically isolated form of Pt with a low valance of +0.75. An electrochemical device that can synthesize H 2 O 2 directly from H 2 and O 2 is fabricated with H 2 O 2 productivity as high as 546 ± 30 mol kg cat − 1 h −1 . The well-defined and high-concentration single atomic Pt sites result in ultrahigh productivity of H 2 O 2 .
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Zehui Fan,Zhisen Li,Dan Mo,Jingyang Zhang,Shuyi Yang,Yun Li,Changlong Bi,Chong Peng,E Tao
Modulation of nano electrocatalysts for targeted excitation of different reactive oxygen species (ROS) is a key challenge to achieve environmentally catalyzed efficient pollutant degradation. In this study, multivalent copper catalysts (Cu (0)/Cu (I)/Cu (II)) load on the surface of biochar (CBX) are prepared by the hydrothermal-impregnation method, and the modulation effect of different valences of copper on the pathway of reactive oxygen species (ROS) generation is investigated. X-ray diffraction (XRD) analysis shows the coexistence of three copper valence states. Radical scavenging experiment and DFT calculations indicate that Cu (I) dominates the adsorption and activation of peroxodisulfate (PS) to efficiently generate ·SO 4 - and ·OH. Cu (II) selectively generates 1 O 2 by modulating the dissolve oxygen conversion pathway; whereas Cu (0) acts as an activation center for bound oxygen and significantly promotes ·O 2 - generation. The nano-electrocatalytic system prepared at 600°C (CB6-PS) degraded 98.3% of enrofloxacin (ENR) over a period of time (60 min). Mechanistic studies indicate that the catalytic system realizes the coupling reaction between the radical pathway (·SO 4 - /·OH /·O 2 - ) and the nonradical pathway ( 1 O 2 ) by the synergistic action of multivalent copper, which providing a new theoretical basis and technical strategy for the development of targeted ROS generation function.
研究领域:
环境催化
·
材料化学
·
污染控制
·
纳米催化
·
环境功能材料
·
高级氧化技术
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Qiming Song,Zifan Li,Qun Peng,Xinwen Ou,Kun Zhao,Zhimin Dong,Liqun Ye,Chenchen Liu,Yunhai Liu,Jun He,Lai-Hon Chung,Bin Han
Photocatalytic O 2 activation, which produces miscellaneous reactive oxygen species (ROSs) via electron or energy transfer, is crucial for various chemical and biological processes. Unfortunately, controlling the exciton behaviors to flexibly regulate the generation of ROSs has rarely been explored and the underlying regulatory mechanisms remain poorly understood. Here, via linkage orientation engineering of covalent organic frameworks (COFs), we showcase a facile strategy for the flexible regulation between 1 O 2 and H 2 O 2 generation in photocatalytic O 2 activation. Imine-based COFs equipped with donor (D)-N=C-acceptor (A) chain (TFPT COFs) exerts effective H 2 O 2 production via electron transfer, while its structurally isomeric COFs with reversed imine orientation (TAPT COFs) tends to singlet oxygen ( 1 O 2 ) photosynthesis via energy transfer, attaining high efficiency for pollutant removal. Based on the results from ultrafast spectroscopy and theoretical calculations, when the N atom of the imine linkage is close to the electron acceptor, it diminishes the surface potential difference and increases the exciton binding energy; this favors the activation of the spin-triplet state excitons via an energy transfer process. Conversely, a strong built-in electric field is created when this N atom is adjacent to the electron donor, which encourages the dissociation of excitons into carriers and their subsequent separation.
研究领域:
化学
·
材料科学
·
生物学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2025
·Vol. 15
·期 6
·544
·
IF 4
Tingting Hu,Baozeng Ren,Liang Zhao
Hydrogen peroxide (H2O2) is an important industrial chemical that is widely applied in many areas. The direct synthesis of H2O2from H2and O2has proved to be a green and economic pathway. Pd-based bimetallic catalysts, due to their superior catalytic performances in this reaction, have attracted intensive attention. Herein, Tetrakis(hydroxymethyl)phosphonium chloride (THPC) was adopted as the protective ligand to immobilize Pd-Au alloy nanoparticles onto activated carbon (AC). The varied Pd/Au molar ratios demonstrated homogeneously distributed Pd-Au nanoalloys with average particle sizes ranging from 3.51 to 5.75 nm. The optimal ratio was observed over the Pd3Au1/AC-THPC catalyst with a maximum H2O2productivity of 165 mol/(kgPd·h) and selectivity of 82.3% under ambient pressure. The relationship between the electronic structure and catalytic activity indicated Pd0was the active site, while the presence of Au inhibited H2O2degradation rate. This research could help in the design efficient bimetallic catalysts for the direct synthesis of H2O2.
研究领域:
化学
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of the American Chemical Society
·
2023
·
IF 15
Shang Shi,Zhenzhen Shen,Shanshan Li,Qian Wang,Rui Wen,Bing Liu
The use of carbon materials in porous electrodes has impressive advantages. However, precisely tailoring the multilevel pore structure of carbon electrodes remains an unsolved challenge. Here, we report a highly efficient site-selective growth strategy to synthesize colloidal carbon rings by templating patchy droplets. Carbon rings are used for the direct fabrication of self-standing porous electrodes with hierarchical pores for lithium–oxygen batteries (LOBs). In situ atomic force microscopy reveals that during discharge the discharge products densely nucleate and grow on carbon rings, demonstrating that such rings are a very potential electrode material in LOBs. The hollow carbon ring electrode (HCRE) possesses micrometer-scale channels formed by random packing of rings and nanochannels consisting of ring-shaped hollow cavities connected by nanosized pores in the wall. Both channels contribute to ion transportation and gas diffusion, but the storage of the discharge products mainly lies in micrometer-scale channels, leading to a high discharge capacity of LOBs (20 658 mAh/g). Our work paves a new way to construct hierarchically porous electrodes for application in electrocatalysis and electrochemical energy storage.
研究领域:
材料科学
·
电化学能源存储
✓ 已验证
DOI
高影响因子
FREE RADICAL BIOLOGY AND MEDICINE
·
2018
·
IF 6.02
Qing Li,Jie Su,Shi-Jie Jin,Wei Wei,Xiao-dong Cong,Xiao-Xue Li,Ming Xu
Background Insulin resistance in endothelial cells contributes to the development of cardiovascular disease in type 2 diabetes mellitus (T2DM). Therefore, there are great potential clinical implications in developing pharmacological interventions targeting endothelial insulin resistance. Our previous studies indicated that argirein which was developed by combining rhein with L -arginine by a hydrogen bond , could substantially relieved stress related exacerbation of cardiac failure and alleviated cardiac dysfunction in T2DM, which was associated with suppressing NADPH oxidase activity. However, it is unclear whether argirein treatment attenuates the vascular lesion and dysfunction in T2DM and its underlying mechanisms. Methods and results The rat aortic endothelial cells (RAECs) were used to treat with palmitic acid (PA), a most common saturated free fatty acid , which could induce insulin resistance. It was showed that argirein increased glucose uptake and glucose transporter-4 (Glut4) expression and reversed the phosphorylation of IRS-1-ser307 and AKT-ser473, consequently resulting in the increase of the production of eNOS and NO in PA-induced RAECs. We further found that argirein blocked the Nox4-dependent superoxide (O 2 -. ) generation, which regulated glucose metabolism in RAECs during PA stimulation. In vitro, argirein increased the release of endothelial NO to relieve the vasodilatory response to acetylcholine and insulin, and restored the expression of Nox4 and pIRS-1-ser307 in the aorta endothelium of high-fat diet (HFD)-fed rats following an injection of streptozocin (STZ). Conclusion These results suggested that argirein could improve endothelial insulin resistance which was attributed to inhibiting Nox4-dependent redox signaling in RAECs. These studies thus revealed the novel effect of argirein to prevent the vascular complication in T2DM.
研究领域:
药理学
·
内分泌学
·
心血管科学
·
糖尿病研究
✓ 已验证
DOI
PubMed
高影响因子
Nano Research
·
2023
·Vol. 16
·期 11
·12697-12705
·
IF 9.9
Gao Xinshuang,Zheng Jia-jia,Li Hanbo,Cai Rui,Gao Xingfa,Wu Xiaochun
Nanozymes, as a novel form of enzyme mimics, have garnered considerable interest. Despite overcoming the main disadvantages of their natural analogs, they still face challenges such as restricted mimic types and low substrate specificity. Herein, we introduce a reactive ligand modification strategy to diversify enzyme mimic types. Specifically, we have utilized helical plasmonic nanorods (HPNRs) modified with para -nitrothiophenol (4-NTP) to create an oxygen-sensitive nitroreductase (NTR) with light-controllability. HPNRs act as a light-adjustable source of nicotinamide adenine dinucleotide/nicotinamide adenine dinucleotide phosphate (NAD(P)H), providing photon-generated energetic electrons to adsorbed 4-NTP molecules. In the presence of O 2 , the activated 4-NTP transfers the captured electron to the adsorbed O 2 , mimicking the electron transfer process in its natural counterpart. This enhanced O 2 activation notably boosts the oxidative coupling of para -aminothiophenol (4-ATP). Density functional theory (DFT) calculations reveal that hot electrons injected into the lowest unoccupied molecular orbital (LUMO) energy level of 4-NTP can be transferred to that of molecular oxygen. In conclusion, our findings underline the potential of the reactive ligand modification strategy in developing new types of enzyme reactions, which opens up promising avenues for the enhancement and diversification of nanozyme functionalities.
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Xiangcheng Zhang,Jingzhen Zhang,Jie Miao,Xue Wen,Chao Chen,Baoxue Zhou,Mingce Long
Photocatalytic H 2 O 2 production is a promising strategy for decentralized applications, but to realize efficient H 2 O 2 production in the ambient conditions and absence of organic sacrifice remains challengeable. Herein, anthraquinone functionalized covalent organic frameworks (TpAQ-COFs) were fabricated by β-ketoenamines links of 2,6-diaminoanthraquinone (AQ) and 2, 4, 6-triformylphloroglucinol (Tp), and the structures and compositions were tuned by controlling the condensation time. The increase of time favors the assembly of TpAQ-COFs into more ordered lamellar stacking structure, and induces the increase of enol-imine form. The critical role of anthraquinone moieties as the active sites for oxygen reduction was proved, that is, facilitating charge separation and enhancing the activity and selectivity of H 2 O 2 production. Upon visible light irradiation, the TpAQ-COF synthesized after 12 h reaction has the highest content of anthraquinone moieties and the best performance for H 2 O 2 production (420 μmol h −1 g −1 ) in the absence of organic sacrificial agents. These findings bring insights to incorporate anthraquinone chemistry into photocatalysts at molecular levels for efficient H 2 O 2 production.
✓ 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）