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NEW JOURNAL OF CHEMISTRY · 2020 ·Vol. 44 ·期 27 ·11808-11816 · IF 3.288

Self-supported beaded Au@Co3O4 nanowire arrays perform electrocatalytic CO2 reduction in water to syngas and water oxidation to O2

Shi-Yuan Zhang,Jing-Jing Ma,Hong-Lin Zhu,Yue-Qing Zheng

Syngas, as a necessary feedstock dependent on non-renewable fossil fuels, is a mixture of CO and H2, which could be prepared by a renewable strategy via electrochemical CO2 reduction in water electrolyte solutions. Herein, beaded Au@Co3O4 nanowire arrays (denoted as Au@Co3O4 NAs) were obtained by immersion in HAuCl4 solution with Co3O4 nanowire arrays. The Au@Co3O4 NAs exhibited outstanding electrochemical performance of producing syngas via tuning from 1 : 1 to 4 : 1 with controlling voltage. In addition, the Au@Co3O4 NAs showed better catalytic performance for the oxygen evolution reaction with an overpotential of 320 mV at a current density of 50 mA cm−2, along with a small Tafel slope of 75 mV dec−1 in 1 M KOH solution. The electrochemical performance of Au@Co3O4 NAs is obviously superior to Co3O4 NAs, which will open up a viable strategy for the design and fabrication of a bi-functional electrocatalyst for the overall reaction (CO2 + H2O → CO + H2 + O2).

研究领域: 材料科学 · 电催化
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Nanoscale · 2019 ·Vol. 11 ·期 31 ·14654-14667 · IF 6.97

MnFe2O4-decorated large-pore mesoporous silica-coated upconversion nanoparticles for near-infrared light-induced and O2 self-sufficient photodynamic therapy

Binbin Ding,Shuai Shao,Haihua Xiao,Chunqiang Sun,Xuechao Cai,Fan Jiang,Xueyan Zhao,Ping'an Ma,Jun Lin

The limited light penetration depth and tumor hypoxia are two natural shortcomings of photodynamic therapy (PDT). Overcoming these two issues within a single system is still a great challenge. Herein, photosensitizer (PS)-loaded and PEG-modified MnFe2O4-decorated large-pore mesoporous silica-coated β-NaYF4:20%Yb,2%Er@β-NaYF4 upconversion nanoparticles (UCMnFe-PS-PEG) as excellent PDT agents are successfully prepared for NIR light-mediated and O2 self-sufficient PDT. The large mesoporous structure observably increases PS loading efficiency (11.33 wt%) and the green luminescence from upconversion nanoparticles activated by NIR is able to activate PSs to generate ROS effectively. In addition, sub-10 nm MnFe2O4 nanoparticles work as a Fenton catalyst to generate O2in situ. In vivo experiments further prove that UCMnFe-PS-PEG not only provides magnetic guidance to the tumor, but also overcomes tumor hypoxia and dramatically enhances PDT efficiency. Furthermore, in vivo MR and UCL imaging are performed for accurate cancer therapy. We believe that the successful construction of the multifunctional UCMnFe-PS-PEG provides more revelations for developing advanced nano-drug systems for cancer therapy.

研究领域: 生物医学工程 · 纳米医学 · 肿瘤治疗
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Journal of Energy Chemistry · 2022 · IF 13.599

Superior oxygen electrocatalyst derived from metal organic coordination polymers by instantaneous nucleation and epitaxial growth for rechargeable Li-O2 battery

Dongdong Li,Jinbiao Chen,Yingtong Chen,Yian Wang,Yanpeng Fu,Minhua Shao,Zhicong Shi

Rechargeable aprotic Li-O 2 batteries have attracted increasing attention due to their extremely high capacity, and it is very important to design appropriate strategies to synthesize efficient catalysts used as oxygen cathode. In present work, we present an expedient “instantaneous nucleation and epitaxial growth” (INEG) synthesis strategy for convenient and large-scale synthesis of ultrafine MOCPs nanoparticles (size 50–100 nm) with obvious advantages such as fast synthesis, high yields, low costs and reduced synthetic steps. The bimetallic Ru/Co-MOCPs are further pyrolyzed to obtain bimetallic Co– and low content of Ru-based nanoparticles embedded within nitrogen-doped carbon (Ru/Co@N C) as an efficient catalyst used in Li-O 2 battery. The Ru/Co@N C provides porous carbon framework for the ion transportation and O 2 diffusion, and has large amounts of metal/nonmetal sites as active site to promote the oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) in Li-O 2 batteries. As a consequence, a high discharge specific capacity of 15246 mA h g −1 at 250 mA g −1 , excellent rate capability at different current densities, and stable overpotential during cycling, are achieved. This work opened up a new understanding for the industrialized synthesis of ultrafine catalysts for Li-O 2 batteries with excellent structural characteristics and electrochemical performance.

研究领域: 材料科学 · 电化学 · 能源存储与转换
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Journal of Materials Chemistry A · 2015 ·Vol. 4 ·期 4 ·1399-1407 · IF 7.443

A graphitic foam framework with hierarchical pore structure as self-supported electrodes of Li–O2 batteries and Li ion batteries

Guangyu Zhao,Li Zhang,Jixian Lv,Changle Li,Kening Sun

Hydrothermal self-assembly is a highly efficient and low cost method to prepare graphitic foam from graphene oxides; however, the self-assembly frameworks usually do not have controllable pore structures because of the spontaneous process. In this paper, a hydrothermal synthesis assisted by ammonium peroxo-polymolybdate [(NH4)2Mo2O11] tailoring to fabricate graphitic foam is presented. The foam possesses pore structures which can be controlled by adjusting the rate of charge in the hydrothermal experiments. Furthermore, the foam obtained from a definite rate of charge [(NH4)2Mo2O11 : graphene oxide is 1 : 2 in weight] has a hierarchical pore structure and a through-hole net. In electrochemical energy storage, such unique features are beneficial for providing efficient mass transport as well as abundant, accessible active sites. The graphitic foam was tested for use as self-supported electrodes of Li–O2 batteries (LOBs) and Li ion batteries (LIBs) without any metallic current collectors or organic binders, and the foam frameworks exhibited remarkable lithium ion storage properties in both of the two batteries (e.g., 5500 mA h g−1 at 0.2 A g−1 as LOB cathodes and 250 mA h g−1 at 50 A g−1 as LIB anodes).

研究领域: 材料科学 · 能源技术
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CHEMICAL RESEARCH IN CHINESE UNIVERSITIES · 2021 ·Vol. 38 ·期 1 ·200-208 · IF 1.307

Nature-inspired Three-dimensional Au/Spinach as a Binder-free and Self-standing Cathode for High-performance Li-O2 Batteries

Wang Yue,Wang Xiaoxue,She Ping,Guan Dehui,Song Lina,Xu Jijing

D esign and fabrication of functional porous air cathode materials with superior catalytic activity is still the key point for non-aqueous lithium-oxygen(Li-O 2 ) batteries. Herein, inspired by the self-standing three-dimensional(3D) structure of the natural spinach leaves, a unique binder-free and self-standing porous Au/spinach cathode for high-performance Li-O 2 batteries has been developed. The carbonized spinach leaves serve as a superconductive current collector and an ideal porous host for accommodating catalysts. The Au/spinach cathode could offer enough spaces for accommodating the discharge products, shorten the distance of the oxygen and electrolyte diffusion, and promote the oxygen reduction reaction(ORR) and oxygen evolution reaction (OER) processes. This optimized Au/spinach cathode achieved a high specific area capacity of 7.23 mA·h/cm 2 at a current density of 0.05 mA/cm 2 and exhibited excellent stability(280 cycles at 0.05 mA/cm 2 with a fixed capacity of 0.2 mA·h/cm 2 ). The superior performance encourages the construction of more advanced cathode architectures by the use of bio-composites for Li-O 2 batteries.

研究领域: 材料科学 · 能源存储 · 电化学
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COMPOSITES PART B-ENGINEERING · 2022 · IF 11.322

Balancing oxygen evolution reaction and oxygen reduction reaction processes in Li–O2 batteries through tuning the bond distances of RuO2

Xinbin Wu,Wei Yu,Wei Xu,Yujun Zhang,Shundong Guan,Zheng Zhang,Shuwei Li,Huanchun Wang,Xuanjun Wang,Liang Zhang,Ce-Wen Nan,Liangliang Li

Lithium-oxygen (Li–O 2 ) batteries are promising next-generation energy storage devices due to their ultrahigh theoretical specific energy. Oxide electrocatalysts such as RuO 2 are often used to improve the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) processes in Li–O 2 batteries, but the relation between the structural parameters and their catalytic properties is unclear so far. In this work, we synthesize RuO 2 nanoparticles at different annealing temperatures and investigate the influence of the Ru–O bond distances of RuO 2 on the OER and ORR processes in Li–O 2 batteries. The results of X-ray absorption fine structure show that the bond distances decrease with the increase of the annealing temperature. The RuO 2 with longer Ru–O bond distances renders a lower charge plateau to Li–O 2 batteries, showing a better OER performance, while that with shorter bond distances gives a larger discharge capacity and is more friendly to the ORR process. The cycle life of Li–O 2 batteries with a carbon nanotube-RuO 2 composite cathode is improved to 287 cycles (1148 h) under an extreme testing condition (the voltage range is 2.3–4.2 V), when the Ru–O bond distances are optimized. In addition, the influence of the Ru–O bond distances on the catalytic properties of RuO 2 is analyzed by density functional theory calculations. The findings in this work provide a guidance to enhance the ORR and OER efficiency of RuO 2 and other oxide catalysts.

CAS / MDL: 872-50-4 1310-73-2
研究领域: 材料科学 · 电化学
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2022 · IF 24.319

Interfacial oxygen vacancies at Co3O4-CeO2 heterointerfaces boost the catalytic reduction of NO by CO in the presence of O2

Shaomian Liu,Wenjuan Xue,Yongjun Ji,Wenqing Xu,Wenxing Chen,Lihua Jia,Tingyu Zhu,Ziyi Zhong,Guangwen Xu,Donghai Mei,Fabing Su

Simultaneously improving both NO x conversion and N 2 selectivity in the selective catalytic reduction of NO by CO (CO-SCR) under O 2 -containing conditions is highly challenging because of the competitive reactions of NO x and CO with O 2 . Here, we demonstrate that the interfacial oxygen vacancies (IOVs) generated at the Co 3 O 4 -CeO 2 heterointerfaces by ball-milling-induced strain can remarkably boost both NO x conversion and N 2 selectivity in the temperature range of 100–400 °C. The Co 3 O 4 -CeO 2 -IOV catalyst achieved approximately 100% NO x conversion and 100% N 2 selectivity (200–350 °C, 1–5 vol% O 2 , and 20,000 h −1 ); even under 10 vol% O 2 , it still showed good catalytic performance. The spectroscopy analysis and theoretical calculations reveal that compared with O 2 activation, IOVs are more favorable for the rate-limiting step of NO adsorption and dissociation. This work provides an effective strategy to create IOVs within metal oxide composite catalysts using ball-milling-induced interfacial strain for improving CO-SCR performance.

CAS / MDL: 10294-41-4
研究领域: 材料科学 · 环境催化 · 化学工程
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CERAMICS INTERNATIONAL · 2022 · IF 5.532

The effect of plasma-assisted ball milling on preparation and sintering behavior of (Zr0.1429Hf0.1429Ce0.1429Y0.2857La0.2857)O2-δ high entropy fluorite oxide

Chufei Cheng,Fengnian Zhang,Fuhao Cheng,Jiadong Hou,Bei Ren,Yang Miao,Libiao Xin,Xiaomin Wang

The sintering process of high entropy fluorite oxide ceramics prepared by the conventional solid-phase reaction method suffers from high single-phase synthesis temperature, low densities, and abnormal grain growth . To improve the sintering characteristics of high entropy fluorite oxide ceramics, the oxide mixture was dealt with dielectric barrier discharge plasma-assisted ball milling. The samples were analyzed using XRD , SEM, TEM, TG/DTG, visual high-temperature deformation analyzer, and nanoindentation meter. The results show that the plasma field activates the raw material powder and promotes powder finer. The rapid heating effect of the plasma during the ball milling process causes micro-area sintering and micro-area melting on the powder surface, which increases the active sites of the solid phase reaction of the material, accelerates the mass transfer process, and improves the sintering activity. Compared with conventional ball milling, plasma-assisted ball milling reduces the single-phase synthesis temperature of high entropy ceramics from 1500 °C to 1300 °C. The sintered ceramic pellets have intact grain growth, no noticeable abnormal grain growth, and improved density and mechanical properties .

CAS / MDL: 1306-38-3
研究领域: 材料科学 · 陶瓷工程
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Carbon Energy · 2023 ·Vol. 5 ·期 8 ·e334 · IF 20.5

Double spatial confinement on ruthenium nanoparticles inside carbon frameworks as durable catalysts for a quasi-solid-state Li–O2 battery

Meiling Wang,Ying Yao,Feiyang Yang,Zhenwu Tang,Jingjie Ren,Cunzhong Zhang,Feng Wu,Xiangke Wang

The rational design of large-area exposure, nonagglomeration, and long-range dispersion of metal nanoparticles (NPs) in the catalysts is critical for the development of energy storage and conversion systems. Little attention has been focused on modulating and developing catalyst interface contact engineering between a carbon substrate and dispersed metal. Here, a highly dispersed ultrafine ruthenium (Ru) NP strategy by double spatial confinement is proposed, that is, incorporating directed growth of metal–organic framework crystals into a bacterial cellulose templating substrate to integrate their respective merits as an excellent electrocatalytic cathode catalyst for a quasi-solid-state Li–O 2 battery. The porous carbon matrix with highly dispersed ultrafine Ru NPs is well designed and used as cathode catalysts in a Li–O 2 battery, demonstrating a high discharge areal capacity of 6.82 mAh cm –2 at 0.02 mA cm –2 , a high-rate capability of 4.93 mAh cm –2 at 0.2 mA cm –2 , and stable discharge/charge cycling for up to 500 cycles (2000 h) with low overpotentials of ~1.4 V. This fundamental understanding of the structure–performance relationship demonstrates a new and promising approach to optimize highly efficient cathode catalysts for solid-state Li–O 2 batteries.

CAS / MDL: 10196-18-6
研究领域: 材料科学 · 电化学 · 能源存储
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MOLECULES · 2022 ·Vol. 27 ·期 17 ·5576 · IF 4.927

Pyropheophorbide-a/(001) TiO2 Nanocomposites with Enhanced Charge Separation and O2 Adsorption for High-Efficiency Visible-Light Degradation of Ametryn

Songtao Liu,Rui Yan,Muhammad Humayun,Huanli Zhang,Yang Qu,Yingxue Jin

It is highly desired to enhance charge separation and O2adsorption of the pyropheophorbide-a (Ppa) to promote visible-light activity and stability. Herein, Ppa modified 001-facet-exposed TiO2nanosheets (Ppa/001T) nanocomposites with different weight ratios were fabricated via the self-assembly approach by OH induced. Compared with the bare Ppa, the 8% amount optimized 8Ppa/001T sample displayed 41-fold enhanced activity for degradation of Ametryn (AME) under visible-light irradiation. The promoted photoactivities could be attributed to the accelerated charge carrier’s separation by coupling TiO2as thermodynamic platform for accepting the photoelectrons with high energy from Ppa and the promoted O2adsorption because of the residual fluoride on TiO2. As for this, a distinctive two radicals (•O2−and •OH) involved pathway of AME degradation is carried out, which is different from the radical pathway dominated by •O2−for the bare Ppa. This work is of utmost importance since it gives us detailed information regarding the charge carrier’s separation and the impact of the radical pathway that will pave a new approach toward the design of high activity visible-light driven photocatalysts.Keywords:Ppa;001-facet-exposed TiO2;charge separation;visible-light photocatalysis;Ametryn

研究领域: 材料科学 · 环境科学 · 光催化
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Acta Biomaterialia · 2023 · IF 9.7

Hyaluronic acid-based supramolecular nanomedicine with optimized ratio of oxaliplatin/chlorin e6 for combined chemotherapy and O2-economized photodynamic therapy

Yuan-Fu Ding,Xun Xu,Junyan Li,Ziyi Wang,Jingwei Luo,Greta S.P. Mok,Shengke Li,Ruibing Wang

Dual- or multi-modality combination therapy has become one of the most effective strategies to overcome drug resistance in cancer therapy, and the optimized ratio of the therapeutic agents working on the tumor greatly affects the therapeutic outcomes. However, the absence of a facile method to optimize the ratio of therapeutic agents in nanomedicine has, at least in part, impaired the clinical potential of combination therapy. Herein, a new cucurbit[7]uril (CB[7])-conjugated hyaluronic acid (HA) based nanomedicine was developed, in which both chlorin e6 (Ce6) and oxaliplatin (OX) were co-loaded non-covalently at an optimized ratio via facile host-guest complexation, for optimal, combined photodynamic therapy (PDT)/chemotherapy. To maximize the therapeutic efficacy, a mitochondrial respiration inhibitor, atovaquone (Ato), was also loaded into the nanomedicine to limit consumption of oxygen by the solid tumor, sparing oxygen for more efficient PDT. Additionally, HA on the surface of nanomedicine allowed targeted delivery to cancer cells with over-expressed CD44 receptors (such as CT26 cell lines). Thus, this supramolecular nanomedicine platform with an optimal ratio of photosensitizer and chemotherapeutic agent not only provides an important new tool for enhanced PDT/chemotherapy of solid tumors, but also offers a CB[7]-based host-guest complexation strategy to facilely optimize the ratio of therapeutic agents for multi-modality nanomedicine. Statement of significance Chemotherapy remains the most common modality for cancer treatment in clinical practice. Combination therapy by co-delivery of two or more therapeutic agents has been recognized as one of the most effective strategies to improve therapeutic outcome of cancer treatment. However, the ratio of loaded drugs could not be facilely optimized, which may greatly affect the combination efficiency and overall therapeutic outcome. Herein, we developed a hyaluronic acid based supramolecular nanomedicine with facile method to optimize the ratio of two therapeutic agents for improved therapeutic outcome. This supramolecular nanomedicine not only provides an important new tool for enhanced photodynamic therapy/chemotherapy of solid tumors, but also offers insights in using macrocyclic molecule-based host-guest complexation to facilely optimize the ratio of therapeutic agents in multi-modality nanomedicine.

研究领域: 纳米技术 · 药学 · 肿瘤学 · 生物医学工程
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Journal of Advanced Ceramics · 2022 ·Vol. 11 ·期 11 ·1801-1814 · IF 11.534

Ti4+-incorporated fluorite-structured high-entropy oxide (Ce,Hf,Y,Pr,Gd)O2−δ: Optimizing preparation and CMAS corrosion behavior

Cheng Fuhao,Zhang Fengnian,Liu Yufeng,Guo Meng,Cheng Chufei,Hou Jiadong,Miao Yang,Gao Feng,Wang Xiaomin

Environmental barrier coatings (EBCs) with excellent chemical resistance and good high-temperature stability are of great significance for their applications in next-generation turbine engines. In this work, a new type of high-entropy fluorite-structured oxide (Ce 0.2 Hf 0.2 Y 0.2 Pr 0.2 Gd 0.2 )O 2− δ (HEFO-1) with different Ti 4+ contents were successfully synthesized. Minor addition of Ti 4+ could be dissolved into a high-entropy lattice to maintain the structure stable, effectively reducing the phase formation temperature and promoting the shrinkage of bulk samples. Heat treatment experiments showed that all the samples remained a single phase after annealing at 1200–1600 °C for 6 h. In addition, high-entropy (Ce 0.2 Hf 0.2 Y 0.2 Pr 0.2 Gd 0.2 Ti 0.2 x )O 2− δ demonstrated great resistance to calcium—magnesium—alumina—silicate (CMAS) thermochemical corrosion. When the content of Ti was increased to x = 0.5, the average thickness of the reaction layer was about 10.5 after being corroded at 1300 °C for 10 h. This study reveals that high-entropy (Ce 0.2 Hf 0.2 Y 0.2 Pr 0.2 Gd 0.2 Ti 0.2 x )O 2− δ is expected to be a candidate for the next-generation EBC materials with graceful resistance to CMAS corrosion.

研究领域: 材料科学 · 涂层 · 高温材料 · 腐蚀抗性
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