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Small · 2024 · IF 13

Heterogeneity in Diameters of Protein Fibrils and Chitosan for a High CO2/O2 Selectivity and Desired Mechanical Properties of Edible Bioplastic Films

Qixin Shi,Yingqun Nian,Yang You,Ziyan Li,Yunqi Li,Ran Zhao,Zhengzhi Chen,Tianhang Huang,Bing Hu

Edible bioplastics offer a possible approach with great potential to address the challenges of plastic and microplastic crisis and the issue of food waste. In the present study, in situ, induction of fibrillation of legume proteins within chitosan matrix is found to form edible bioplastic films with a high CO 2 /O 2 selectivity coefficient of ≈130. Desirable mechanical properties, including a high elongation at break of ≈230%, are realized to fabricate shopping bags, which can be filled with 5 kg of fruits. An atmosphere with a high CO 2 content and low O 2 concentration is spontaneously achieved after strawberries are packaged with the films and ≈85% of the fruits are edible after 9 days. The contents of CO 2 in the equilibrium state and the percent of edible fruits are positively correlated with the CO 2 /O 2 selectivity of the films. By comparison of the edible bioplastic films made from mung bean protein (MP) and pea protein (PP), the fibrillation capability of legume proteins and the heterogeneity in polydisperse diameters of the protein fibrils and chitosan are demonstrated to make great contributions to the dense microstructure, leading to the strong mechanical properties and high gas selectivity of the films. The structure-property relationship is elucidated for high-performance bioplastics films.

CAS / MDL: 2390-54-7
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JOURNAL OF THE EUROPEAN CERAMIC SOCIETY · 2024 · IF 5.8

Ti4+ doped high-entropy fluorite oxide ceramics ((ZrHfCeYEr)(1-x)/5Tix)O2-δ: Thermal, mechanical and cyclic thermal shock resistance properties studies

Bei Ren,Ziqian Meng,Bixian Zhang,Sihao Jian,Chufei Cheng,Jiadong Hou,Ruixin Hao,Bo Li,Yang Miao,Chao Ma,Weihua Ji

High-entropy fluorite oxide ceramics are promising candidates for spacecraft applications due to their excellent high-temperature thermal-mechanical properties. In this work, four kinds of high-entropy fluorite oxide ceramics ((ZrHfCeYEr) (1-x)/5 Ti x )O 2-δ (HEFOs, x = 0, 0.025, 0.05, 0.075) with different Ti 4+ contents were successfully synthesized through solid-state reaction method with conventional sintering. They all exhibited phase stability when annealed at 1500 ℃ for 20 h. When the content of Ti 4+ was increased to x = 0.075, the thermal conductivity reduced to1.34 W·m −1 ·K −1 at 1100 ℃, and the hardness and elastic modulus increased to 14.01 GPa and 205.70 GPa, respectively. Furthermore, the cyclic thermal shock resistance of HEFOs at different temperatures was investigated. The initial flexural strength reached 219.03 MPa when the content of Ti 4+ was increased to x = 0.075. After 60 thermal shock cycles at 1200 ℃ and 1500 ℃, the residual strength ratios were 97.56 % and 83.36 %, respectively. The results of this study establish the foundation for future applications of high-entropy fluorite oxide ceramics in spacecraft hot-end components.

CAS / MDL: 13463-67-7
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JOURNAL OF CATALYSIS · 2024 · IF 6.5

Unveiling the significant promoting effect of SO2 on Ir/SiO2 catalyst for the CO-SCR of NOx in the presence of O2

Ruoyuan Li,Aixia Li,Junhua Li,Yao Wang,Zhiming Liu

Selective catalytic reduction of NO x by CO (CO-SCR) in the presence of O 2 is challenging because in this process CO is prone to being oxidized by O 2 , thus inhibiting NO x reduction by CO. Furthermore, SO 2 typically leads to the deactivation of the CO-SCR catalyst. Herein, a significant promoting effect of SO 2 on Ir/SiO 2 catalyst for the CO-SCR of NO x in the presence of O 2 is reported. In-situ X-ray Absorption Fine Structure (XAFS) and X-ray photoelectron spectroscopy (XPS) analysis showed that SO 2 does not affect the chemical nature of Ir 0 under reaction conditions. However, SO 2 can be oxidized to sulfate and deposit on the catalyst surface. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis demonstrated that the presence of SO 2 can inhibit the CO + O 2 reaction, thus leaving more CO available to reduce NO x over the active Ir 0 sites. As a result, the reduction of NO x is remarkably promoted even in the presence of O 2 and SO 2 .

CAS / MDL: 10025-83-9
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ENVIRONMENTAL TECHNOLOGY · 2015 · IF 1.56

Effect of HCl/SO2/NH3/O2 and mineral sorbents on the partitioning behaviour of heavy metals during the thermal treatment of solid wastes

Qunxing Huang,Xu Cai,Moussa Mallaye Alhadj Mallah,Yong Chi,Jianhua Yan

The high concentration of heavy metals in solid wastes may cause serious pollution during thermal treatment. We have investigated, theoretically and experimentally, the effects of several important flue gas species and mineral sorbents on the partitioning behaviour of four major heavy metals (cadmium, lead, zinc and copper) which are often present in municipal solid waste (MSW). Their concentrations in bottom ash, fly ash and flue gas were quantified when model MSW samples were treated thermally under different conditions. The evaporation ratio of the four metals, excluding Cu, increased with decreasing oxygen concentration. The presence of HCl promotes heavy metal evaporation by preventing the formation of stable metallic species, especially for Zn (evaporation of more than 20%). An increase in oxygen concentration has a negative influence on the effect of HCl. In the presence of SO2, Cd and Pb exhibited a higher evaporation ratio, while Zn and Cu were insensitive to the change. SO2 also inhibits Cd vaporization in an oxidative atmosphere. The effect of NH3 on reducing the metal volatilization rate was established indirectly. Calcium oxide addition enhances metal evaporation except for that of Zn (which shows a decrease of 38%). Although desulphurization by calcium injection decreases the volume of acid gas, calcium affects heavy metal pollution control adversely. The presence or addition of SiO2- or Al2O3-containing minerals can lead to the formation of stable metallic salts. This may favour the control of Cd, Pb, Zn and Cu volatilization up to 13%, 50%, 17.5% and 19%, respectively.

研究领域: 环境科学 · 废物处理
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Molecular Catalysis · 2020 · IF 3.687

Efficient and selective oxidation of secondary benzylic CH bonds to ketones with O2 catalyzed by metalloporphyrins under solvent-free and additive-free conditions

Hai-Min Shen,Lei Liu,Bei Qi,Meng-Yun Hu,Hong-Liang Ye,Yuan-Bin She

Non-solvent and non-additive oxidation of secondary benzylic C–H bonds to aromatic ketones utilizing simple metalloporphyrins as catalysts and O 2 was investigated systematically. Based on systematical studies on reaction parameters, such as the structures of porphyrins, the types of central metals, the amount of catalyst, the pressure of oxygen, and the temperature, most aromatics with secondary benzylic C–H had been converted efficiently and selectively to their corresponding aromatic ketones catalyzed by the optimized metalloporphyrin catalyst T(2,3,6-triCl)PPCo. And the selectivity towards aromatic ketones reached up to 80 %–95 % with acceptable conversions in lower catalyst-loading (2.4 × 10 −3 %, mol/mol). The highest selectivity was achieved for substrate 1,2,3,4-tetrahydronaphthalene with the selectivity of 95.0 % in the conversion of 46.3 %. The superior catalytic performance of T(2,3,6-triCl)PPCo could be mainly ascribed to its excellent plane structure, superior ability for electron transfer and low positive charge around the central metal. All of above properties promoted the formation of catalytic active species high-valence cobalt-oxo complexes, and facilitated the approach of substrates to the catalytic active centers. This work presented an optimized balance among higher selectivity, milder conditions, lower catalyst-loading, and simpler catalysts compared with current documents, which was not only an efficient, practical and significant strategy to functionalize the widely available aromatics possessing secondary benzylic C H with high efficiency and selectivity under milder conditions, but also an important instance in the effective functionalization and utilization of other C H bonds employing optimized catalytic systems based on metalloporphyrins.

研究领域: 有机化学 · 催化化学
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CHEMICAL ENGINEERING JOURNAL · 2026 · IF 12.5

Layered-confinement steering of single-atom Fe-N3O1 sites in carbon nitride for peroxymonosulfate activation: Tuning coordination geometry toward 1O2/•O2− selective generation

Yingying Zhang,Qiang Huang,Ruoting Wang,Xinjie Du,Yu Yu,Zhe Chen

Modulating the coordination environment of single-atom catalysts (SACs) and designing architectures to maximize the exposure of active sites are pivotal strategies for enhancing peroxymonosulfate (PMS) activation. The fabrication of single-atom‑iron catalysts on support with particular coordination is essential but still remains challenge. Herein, we proposed the construction of single-atom‑iron embedded in graphitic carbon nitride nanosheets (SA-Fe@C 3 N 4 ) catalyst. The layer-confined synthesis strategy realized the loading of single-atom irons and ultrathin C 3 N 4 nanosheet formation in the interlayer of layered template RUB-15. XANES analysis corroborated that the isolated iron atoms are coordinated with three nitrogen and one oxygen atoms (Fe-N 3 O 1 ). Notably, the single iron atoms within the SA-Fe@C 3 N 4 matrix serve as the predominant active sites for PMS activation. The catalyst exhibited exceptional activity for the degradation of sulfamethoxazole (SMX), achieving a mass-normalized rate constant ( k Fe ) of 1.54 × 10 5  min −1  mol −1 with high selectivity toward 1 O 2 /•O 2 − .Theoretical calculations revealed that the Fe-N 3 O 1 moiety accelerated the PMS adsorption and reduced energy barriers for the activation of PMS, thus produce key *O intermediate SO 5 •- and form 1 O 2 /•O 2 − with nearly 100% selectivity. This study supplied a simple avenue to fabricate single-atom‑iron on C 3 N 4 with regulated coordination for wastewater treatment.

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ENVIRONMENTAL SCIENCE & TECHNOLOGY · 2025 · IF 11.3

Intensifying the Oxide–Support Electronic Interaction via Zinc Doping to Boost Catalytic N2O Decomposition in the Presence of O2 for Co3O4/CeO2 Catalysts

Hao Liu,Siqing Cheng,Jianjun Chen,Xiaoping Chen,Shangchao Xiong,Fang Huang,Houfeng Liu,Junhua Li,Chuanzhi Sun

Mitigating industrial nitrous oxide (N2O) emissions is critical for climate action, yet developing efficient low-temperature N2O decomposition catalysts under O2-containing conditions remains challenging. The weak oxygen–support interaction leads to unsatisfactory N2O decomposition performance in the supported Co3O4/CeO2 catalyst. This study aims to enhance the electronic oxide–support interaction in the Co3O4/CeO2 catalyst through Zn doping, thereby improving its catalytic performance for N2O decomposition under O2-rich conditions. The results demonstrate that, in the presence of 5% O2, the activation energy of the catalyst sharply decreases from 117.5 to 60.4 kJ·mol–1 after Zn doping (Co2.4Zn0.6O4/CeO2). Additionally, the doped catalyst exhibits strong durability to the O2 + H2O + NOx impurity gas components. Advanced spectral characterization and density functional theory calculations reveal that Zn doping modulates the geometry and electronic structure of active cobalt sites, optimizing the adsorption and activation capabilities of N2O molecules. This study elucidates the mechanism of N2O decomposition over the catalysts and establishes a clear structure–activity relationship between the atomic-scale configuration of active sites and their performance. These findings provide critical insights for designing efficient supported oxide catalysts through targeted doping strategies and offer new perspectives for developing highly efficient and low-energy N2O decomposition catalysts.

CAS / MDL: 10294-41-4
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Decomposition mechanism of Cl-VOCs on Cu- and Fe-modified activated carbon in an O2-free atmosphere: The oxidation pathway and product distribution

Yuran Li,Zhicheng Xu,Jian Wang,Bin Wang,Tingyu Zhu

Activated carbon exhibits a high adsorption capacity for chlorinated volatile organic compounds (Cl-VOCs), while the desorption of Cl-VOCs is not desirable in the thermal regeneration progress of activated carbon. Chlorobenzene was selected as the model substance to explore whether Cl-VOCs can be oxidized as expected in the regeneration atmosphere of O 2 -free at the temperature range of 150–450 °C. The modification of activated carbon by Cu or Fe has been shown to considerably improve the decomposition activities. According to the breakthrough curves and detection results from XPS and in situ DRIFTS, the decomposition mechanism of C 6 H 5 Cl on Cu and Fe active sites is illustrated. The adsorbed C 6 H 5 Cl is firstly dechlorinated to form C 6 H 6 and *Cl, and then it was found there are two pathways for the C 6 H 6 oxidation. C 6 H 6 is indirectly oxidized to form C 6 H 5 OH and benzoquinone species, or directly ring-opened to generate ethylene and 1,3-butadiene, and further oxidized to produce CO 2 , CO and H 2 O. The C 6 H 6 oxidation is determined by the decomposition of acetate on Cu/AC, but the decomposition of benzoquinone and maleate on Fe/AC. The Fe 3 O 4 and Fe 2 O 3 active sites have a higher dechlorination activity but accelerate the deposition of FeCl 2 , FeCl 3 and organic Cl-containing components. The CuO active center has a higher oxidation performance with a higher CO 2 selectivity. About 83.0–83.5% of adsorbed chlorobenzene has been oxidized, and the main Cl-containing product is HCl accounting for approximately 77.8–81.0%, a small amount of Cl forms polychlorinated organic compounds or metal chlorides occupying 2.0–5.7%. As the regeneration temperature decreases, the total amount of Cl-containing species is reduced due the lower oxidation and dechlorination activity of catalysts. The decomposition products of Cl-VOCs in the thermal regeneration process of activated carbon were clarified and quantified, which provides a theoretical basis to control Cl-VOCs in regeneration gas.

CAS / MDL: 10031-43-3 7782-61-8
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Tailoring the three-phase microenvironment surface to induce carbon nitride oxide generating ·O2– with 100% selectivity for ultrafast photodegradation tetracycline under visible light

Xingyu Zhan,Yunxiong Zeng,Jingcai Xu,Yingchun Xia,Xinqing Wang,Fang Tao,Jie Ouyang,Hongliang Li,Liming Yang,Shenglian Luo,Bo Hong

The reactive oxygen species (ROS) contribute to photodegrading tetracycline (TC), which determines the overall efficiency of photocatalysts. Superoxide radical (·O 2 – ) is one of the excellent ROS for photodegrading TC by carbon nitride. However, achieving hierarchical carbon nitride with efficient, stabile, and selective production of ·O 2 – via O 2 photoreduction is a great challenge. Herein, a carbon nitride oxide nest (CNON 6 ) with carbon/nitrogen vacancies (C-v, N-v) and oxygen substitution (O-s) was prepared via tailoring surface microenvironment. The CNON 6 can photodegrade 82% of TC within 2 min under visible light, and the pseudo-first-order kinetic constant is 1.22 min −1 , 24-fold higher than that of CN. The superior photoactivity is attributed to a unique surface microenvironment, which N-v increased photoelectric conversion efficiency, C-v enhanced O 2 adsorption and O-s induced ·O 2 – evolution with ∼ 100% selectivity. Moreover, PVDF membrane-supported CNON 6 (11.33 cm 2 , 0.88 mg/cm 2 ) can completely remove TC from wastewater at a rate of 2.62 mg/h in a simulated industrial continuous flow cell. The cost-effectiveness assessment was $6.36/kg/h, implying the CNON 6 /PVDF has a bright application prospect in wastewater treatment. This work developed a surface microenvironment tailor strategy to design photocatalysts for efficient degradation of TC.

CAS / MDL: 57-13-6 298-83-9 64-75-5
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ELECTROANALYSIS · 2018 ·Vol. 30 ·期 6 ·1033-1040 · IF 2.851

Online Electrochemical Monitoring of Glucose in Rat Brain with Acanthosphere-like CuOOH Nanospheres-based Electrochemical Sensor as Non-enzymatic and O2-independent Detector

Bo Li,Yongzhao Fan,Changqing Li,Xu Zhao,Kun Liu,Yuqing Lin

This study for the first time establishes a reliable non-enzymatic online electrochemical system (OECS) for selective and continuous measuring glucose in animal cerebral system. We proposed a one-step electrochemical method to synthetize a Cu nanostructure directly onto electrode, and over-oxidize it in NaOH to form acanthosphere-like CuOOH nanospheres (denoted as AN-CuOOH), which can serve as an excellent electrochemical catalyst for glucose oxidation and thus for simple and reproducible non-enzymatic glucose detection in strong alkaline solution. To validate the AN-CuOOH-based sensors for in vivo applications, we connect the sensors to a merged solution of in vivo microdialysis and 0.4 M NaOH to set up an OECS for in vivo glucose monitoring in rat brain. The response of this system has strong tolerance to the oxygen and pH fluctuation which may happen in the cerebral brain system during some physiological and pathological processes. The fabricated non-enzymatic OECS has a good linear current response to glucose within a concentration range from 10 to 1000 μΜ with sensitivity of 130.22 nA ⋅ μΜ −1 cm −2 . Additionally, the OECS is stable and does not suffer from the interference coexisting in the cerebral system. With the fabricated non-enzymatic OECS for glucose measurement, the basal level of glucose in the microdialysate from rats striatum was determined to be 248.63 μΜ (n=3). Furthermore, the glucose was clearly decreased to 26.37 % of the basal level when the rat was undergone by 20 min ischemia, and the glucose concentration was gradually restored to 99.15 % during 40 min of reperfusion. Our work propose a technically simple strategy for the fabrication of a highly reproducible non-enzymatic OECS system free from oxygen and pH interference, which is promising in exploring the molecular mechanism associated with brain functions.

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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Mixed-ligand metal–organic frameworks with coordinatively un-saturated Co(II) and Ni(II) sites for regenerable O2-selective ad-sorption over N2

Hanbang Liu,Liping Yang,Danhua Yuan,Guangye Liu,Jiacheng Xing,Yunpeng Xu,Zhongmin Liu

For air separation, the separation method relying on adsorbents has attracted wide attention as a low energy consumption process, and the development of O 2 -selective adsorbents is of great significance. Metal-organic frameworks with coordinatively unsaturated transition metal sites have great potential in O 2 -selective adsorption, but most of them cannot be completely regenerated at ambient temperature or can only be effective at very low temperatures. Herein, we report two mixed-ligand metal–organic framework adsorbents [M(AIP)(BPY) 0.5 ·H 2 O] n ·2nH 2 O with coordinatively unsaturated cobalt(II) and nickel(II) sites, which can preferentially adsorb O 2 versus N 2 , and their IAST O 2 /N 2 selectivities are both significantly greater than 1 at 25 °C. These materials exhibited excellent stability and had no loss of adsorption capacities even after immersion in water for 7 days. More importantly, O 2 adsorption–desorption cycle experiments showed that these adsorbents can be completely regenerated at ambient temperature after adsorbing O 2 , and the breakthrough experiments further confirmed their dynamic O 2 /N 2 separation potential and regeneration ability. The results of theoretical calculations suggested that the interactions between adsorbents and O 2 are stronger than those of N 2 , and they have relatively obvious differences in the N 2 and O 2 interaction energies. This work provides inspirations for searching for metal–organic frameworks that can selectively adsorb O 2 at ambient temperature.

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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

A bifunctional MnxCo3-xO4-decorated separator for efficient Li-LiI-O2 batteries: A novel strategy to promote redox coupling and inhibit redox shuttling

Dan Li,Ziye Kang,Hao Sun,Ying Wang,Haiming Xie,Jia Liu,Jiefang Zhu

Although redox mediator (RM) strategy can decrease the overpotential in Li-O 2 batteries by tuning the electrochemical formation/degradation of Li 2 O 2 from the circumscribed surface pathway to the solution one, the redox shuttling causes an unexpected RM degradation and a continuous deterioration of Li anode, finally leading to a poor cyclability. This work presents the first report detailing the development of a novel Mn x Co 3-x O 4 -decorated separator for Li-LiI-O 2 batteries. Benefiting from the promotion effect of Mn x Co 3-x O 4 nanocages on I − /I 3 − and I 3 − /I 2 redox coupling, the cell with as-prepared separator maintains a low charge potential of ~3.3 V till the death of cell cycling. In addition, as-prepared separator can efficiently restrain the redox shuttling, leading to an obvious improvement on cycling stability for the cell. Moreover, the contributions of LiI to the battery performance and the operation mechanism are systematically investigated. These results present a promising progress in the development of multi-functional separator materials for RM-involved Li-O 2 batteries and the new design of hybrid energy storage device.

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