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ACS Applied Energy Materials · 2022 · IF 6.959

Evaluation of Thermochemical Energy Storage Performance of Fe-/Mn-Doped, Zr-Stabilized, CaO-Based Composites under Different Thermal Energy Storage Modes

Jian Sun,Shengbin Bai,KeKe Li,Yue Zhou,Yuning Chen,Lei Liu,Zijian Zhou

CaCO3/CaO materials possess the advantages of low cost, high energy storage density, and working temperature, which offer these materials the potential to be used in thermochemical energy storage systems for concentrated solar power plants. However, CaCO3/CaO materials possess poor antisintering and optical absorption abilities, largely limiting their practicability for direct solar utilization. In this study, binary ion doping of Fe/Mn and Zr-based stabilizer incorporation were simultaneously conducted to improve the cyclic thermal energy storage/release performance of CaCO3/CaO materials. The spectral absorbance of synthetic CaO-based composites (ranging from 77.8% to 84.0%) doped with binary ions of Fe/Mn is greatly increased in comparison to that of pure CaO (∼12.2%) due to the generation of black Ca2Fe2O5 and Ca4Mn3O10. The cyclic thermal energy storage/release performances of synthetic CaO-based composites were comparatively investigated under two thermal energy storage modes (CSP-N2 and CSP-CO2). The Zr-doped, CaO-based composites exhibit a cycling stability superior to those of Zr-free CaO-based composites due to the generated inert CaZrO3 with desirable antisintering ability, and the superiority is more prominent under CSP-CO2 mode. After 50 cycles, the CaO-based composite with a molar ratio of Ca:Zr = 100:6.7 exhibits a remarkably stable energy release density of 1.02 MJ/kg under CSP-CO2 mode, retaining 88.9% of its initial energy release density.

CAS / MDL: 5949-29-1
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CHINESE JOURNAL OF STRUCTURAL CHEMISTRY · 2022 · IF 0.847

Syntheses, Crystal Structures and DNA-Binding Properties of Zn(II) and Mn(II) Complexes Based on Imidazole Derivatives and Carboxylic Acid

Hui-Chao GUAN,Xiao-Tong SONG,Gui-Bao LIU,Shu-Mei YUE

Complexes [Zn(pbm)(5-hip)3] ( 1 ), [Zn(pbm)(5-nip) 3 ] ( 2 ), [Mn(pbm)(H 3 btc) 2 (H 2 O)] ( 3 ) and [Mn(pbm)(5-nip) 3 ] ( 4 ), where H 2 HIPA = 5-hydroxyisophthalic acid, H 2 nip = 5-nitroisophthalic acid, H 3 btc = trimesic acid and pbm (pyridine benzene chelate material) = 2-(2-pyridyl)benzimidazole, were identified via single-crystal XRD analyses. 1, 2 and 4 pertain to the monoclinic space group C 2/ c , while 3 belongs to the triclinic space group P ① . The interplay of CT-DNA with those complexes was delineated using ultraviolet, fluorescence, and circular dichroism (CD) spectroscopy and viscosity measurements. Complexes 1, 2, 3 and 4 interact with CT-DNA in an electrostatic or grooving mode. We wish to offer a theory-wise foundation for developing anti-tumor medicines.

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JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY · 2022 ·Vol. 97 ·期 5 ·1293-1304 · IF 3.709

Production of NMSBA catalyzed by Co/Mn/Br together with the porous carbon made from coconut shell with ZnCl2 as activator

Le-Yao Wang,Zhen Yang,Feng Guo,Xiang-Li Long

BACKGROUND 2-nitro-4-methylsulfonylbenzoic acid (NMSBA) is commercially produced from the oxidation of 2-nitro-4-methylsulfonyltoluene (NMST) with nitric acid as oxidant and V 2 O 5 as catalyst in a strong acid solution; this process suffers from the following shortcomings: the discharge of large amounts of wastewater and waste gas, as along with the generation of polynitro compounds. It is necessary to develop a technology to avoid the pollution caused by oxidizing NMST with nitric acid. NMSBA can be synthesized by oxidizing NMST with air under the catalysis of the porous carbon made from coconut shell with ZnCl 2 as an activator together with Co/Mn/Br. RESULTS The optimum conditions for the preparation of the porous carbon are as follows: impregnation temperature 60 °C, ZnCl 2 concentration 0.50 mol L −1 , impregnation duration 6 h, carbonization temperature 600 °C, and carbonization time 4 h. The surface characterization suggests that the carbon made in this study holds smaller surface area, acidic groups, and basic groups than the commercial carbon but owns more carboxyl. CONCLUSION The Co/Mn/Br/AC (AC,the porous carbon made in this study) catalytic system is superior to the Co/Mn/Br/H 3 PMo 12 O 40 @CAC(CAC,commercial activated carbon) catalytic system in the production of NMSBA from the oxidation of NMST. The NMSBA selectivity gained by the former is 93.40%, while that gained by the latter is 87.14%. The former can cut down the consumption of NMST and the expenditure of catalysts. The catalytic ability of the AC catalyst relies on its surface chemical characteristics and physical properties. More carboxyl on AC is the reason for the upgrade of NMSBA selectivity. © 2022 Society of Chemical Industry (SCI).

CAS / MDL: 6147-53-1 6156-78-1
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Journal of Energy Chemistry · 2023 · IF 13.1

Heteroatom anchors Fe-Mn dual-atom catalysts with bi-functional oxygen catalytic activity for low-temperature rechargeable flexible Zn-air batteries

Yuting He,Hongtao Li,Yi Wang,Yufei Jia,Yongning Liu,Qiang Tan

M−N−C (M = Fe, Co, Ni, etc.) catalyst owns high catalytic activity in the oxygen catalytic reaction which is the most likely to replace the Pt-based catalysts. But it is still a challenge to further increase the active site density. This article constructs the high-efficiency FeMn-N/S-C-1000 catalyst to realize ORR/OER bifunctional catalysis by hetero-atom, bimetal (Fe, Mn) doped simultaneously strategy. When evaluated it as bi-functional electro-catalysts, FeMn-N/S-C-1000 exhibits excellent catalytic activity ( E 1/2  = 0.924 V, E j =10  = 1.617 V) in alkaline media, outperforms conventional Pt/C, RuO 2 and most non-precious-metal catalysts reported recently. Such outstanding performance is owing to N, S co-coordinated with metal to form multi-types of single atom, dual atom active sites to carry out bi-catalysis. Importantly, nitrite poison test provides the proof that the active sites of FeMn-N/S-C are more than that of single-atom catalysts to promote catalytic reactions directly. To better understand the local structure of Fe and Mn active sites, XAS and DFT were employed to reveal that FeMn-N 5 /S-C site plays the key role during catalysis. Notably, the FeMn-N/S-C-1000 based low-temperature rechargeable flexible Zn-air also exhibits superior discharge performance and extraordinary durability at −40 °C. This work will provide a new idea to design diatomic catalysts applied in low-temperature rechargeable batteries.

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JOURNAL OF MOLECULAR LIQUIDS · 2023 · IF 6

Performance and mechanism of efficient activation of peroxymonosulfate by Co-Mn-ZIF derived layered double hydroxide for the degradation of enrofloxacin

Yiqiong Yang,Borui Jie,Yixuan Zhai,Yijie Zeng,Jingyan Kang,Geng Cheng,Xiaodong Zhang

Due to the uncontrolled synthesis of layered double hydroxides (LDHs), a simple and efficient strategy was needed to construct high-performance LDHs. Herein, Co-Mn-ZIF was used as the sacrificial template to form cobalt-manganese-nickel LDH (M−Co−Mn−Ni LDH) through the process of deconstruction and reconstruction. Due to the sufficient in-situ etching of the Co-Mn-ZIF template, M−Co−Mn−Ni LDH exhibited a larger specific surface area (482.4 m 2 /g) and pore volume (3.3 × 10 −2 cm 3 /g) as well as easier diffusion and interaction with reaction sites of organic molecules. The prepared M−Co−Mn−Ni LDH showed high catalytic performance for the degradation of enrofloxacin (ENR) by activating peroxymonosulfate (PMS), with the removal rate of 88.5 % within 30 min. The quenching reaction and electron paramagnetic resonance (EPR) analysis results indicated that SO 4 •− and 1 O 2 were main active substances in the oxidation process of ENR. In addition, the Co-Mn-Ni LDH/PMS system was stable and almost unaffected by pH values, organic and inorganic substances, and it could achieve high removal efficiency in various pollutant samples. This work provided a convenient and efficient approach for the construction of high-performance MOFs derived LDHs catalysts.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2023 · IF 9.9

Boosting oxygen reduction via MnP nanoparticles encapsulated by N, P-doped carbon to Mn single atoms sites for Zn-air batteries

Xiaoyun Zhang,Fan Yang,Siyuan Sun,Kexin Wei,Hongchen Liu,Guohua Li,Yang Sun,Xi Li,Jinxiu Qian,Shaoxiong Du,Mingjie Li,Yi Lu,Chuangui Xia,Sai Che,Yongfeng Li

An electrocatalyst of single-atomic Mn sites with MnP nanoparticles (NPs) on N, P co-doped carbon substrate was constructed to enhance the catalytic activity of oxygen reduction reaction (ORR) through one-pot in situ doping-phosphatization strategy. The optimized MnSA-MnP-980℃ catalyst exhibits an excellent ORR activity in KOH electrolyte with a half-wave potential (E 1/2 ) of 0.88 V (vs. RHE), and the ORR current density of MnSA-MnP-980℃ maintained 97.9 % for over 25000 s chronoamperometric i-t measurement. When using as the cathode, the MnSA-MnP-980℃ displays a peak power density of 51 mW cm −2 in Zinc-Air batteries, which observably outperformed commercial Pt/C (20 wt%). The X-ray photoelectron spectroscopy reveal that the doped P atoms with a strong electron-donating effectively enhances electron cloud density of Mn SAs sites, facilitating the adsorption of O 2 molecules. Meanwhile, the introduction of MnP NPs can regulate the electronic structure of Mn SAs sites, making Mn SAs active sites exist in a low oxidation state and are less positively charged, which can supply electrons for ORR process to narrow the adsorption energy barrier of ORR intermediates. This work constructs novel active sites with excellent ORR properties and provides valuable reference for the development of practical application.

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FUEL · 2023 · IF 7.4

Promoting effect of Cu and Mn doping on the Fe/ZSM-5 catalyst for selective catalytic reduction of NO with NH3

Yuheng Qiao,Zhenzhen Guan,Mengyan Zhang,Gan Chen,Shifeng Zhou,Hailong Liu,Jiang Wu,Ruitang Guo,Weiguo Pan,Fangqin Li,Ping He

In this paper, a series of Fe-based catalysts with Zeolite Socony Mobil-5 (ZSM-5) as supports were synthesized using the sol–gel method to obtain the Fe/ZSM-5, Mn-Fe/ZSM-5, Cu-Fe/ZSM-5 and Cu-Mn-Fe/ZSM-5 catalysts. The synthesized catalysts were examined and characterized via catalytic activity testing, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N 2 adsorption/desorption, scanning electron microscope (SEM), temperature-programmed desorption of NH 3 (NH 3 -TPD), temperature-programmed reduction with H 2 (H 2 -TPR) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The results showed that the Cu-Mn-Fe/ZSM-5 catalyst had the best catalytic performance compared with the other catalysts. In addition, Fe/ZSM-5 and Cu-Mn-Fe/ZSM-5 all exhibited excellent stability as well as good tolerance to SO 2 & H 2 O under the experimental conditions. Further characterization results showed that with co-doping of Cu and Mn, the amount of Mn 4+ , Cu + , Fe 3+ and surface chemisorbed oxygen (O β ) on the surface of Fe/ZSM-5 increased, promoting the catalytic performance. The DRIFT studies revealed that the NH 3 -SCR reaction followed both the E-R and L-H mechanism on the surface of the Fe-based ZSM-5 catalyst. The Fe-based ZSM-5 catalyst is a good candidate for NH 3 -SCR both in high reactivity and outstanding stability.

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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES · 2023 ·Vol. 24 ·期 18 ·14085 · IF 5.6

Hierarchical Ni-Mn LDHs@CuC2O4 Nanosheet Arrays-Modified Copper Mesh: A Dual-Functional Material for Enhancing Oil/Water Separation and Supercapacitors

Yue Wu,Guangyuan Lu,Ping Xu,Tian C. Zhang,Huaqiang He,Shaojun Yuan

The pursuit of superhydrophilic materials with hierarchical structures has garnered significant attention across diverse application domains. In this study, we have successfully crafted Ni-Mn LDHs@CuC2O4nanosheet arrays on a copper mesh (CM) through a synergistic process involving chemical oxidation and hydrothermal deposition. Initially, CuC2O4nanosheets were synthesized on the copper mesh, closely followed by the growth of Ni-Mn LDHs nanosheets, culminating in the establishment of a multi-tiered surface architecture with exceptional superhydrophilicity and remarkable underwater superoleophobicity. The resultant Ni-Mn LDHs@CuC2O4CM membrane showcased an unparalleled amalgamation of traits, including superhydrophilicity, underwater superoleophobicity, and the ability to harness photocatalytic forces for self-cleaning actions, making it an advanced oil-water separation membrane. The membrane’s performance was impressive, manifesting in a remarkable water flux range (70 kL·m−2·h−1) and an efficient oil separation capability for both oil/water mixture and surfactant-stabilized emulsions (below 60 ppm). Moreover, the innate superhydrophilic characteristics of the membrane rendered it a prime candidate for deployment as a supercapacitor cathode material. Evidenced by a capacitance of 5080 mF·cm−2at a current density of 6 mA cm−2in a 6 M KOH electrolyte, the membrane’s potential extended beyond oil-water separation. This work not only introduces a cutting-edge oil-water separation membrane and supercapacitor electrode but also offers a promising blueprint for the deliberate engineering of hierarchical structure arrays to cater to a spectrum of related applications.Keywords:superwetting mesh;self-cleaning;oil/water separation;supercapacitors

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ENVIRONMENTAL POLLUTION · 2021 · IF 8.071

A novel modified Fe–Mn binary oxide graphite felt (FMBO-GF) cathode in a neutral electro-Fenton system for ciprofloxacin degradation

Anqi Huang,Dan Zhi,Yaoyu Zhou

A graphite felt (GF) cathode was firstly modified by Fe–Mn binary oxide (FMBO), active carbon (AC), carbon black (CB), and polytetrafluoroethylene (PTFE), which exhibits satisfactory ciprofloxacin (CIP) removal efficiency at neutral pH value in electro-Fenton (EF) system. Morphological data showed that modified cathodes have larger surface area and volume pore as well as more active sites. And electrochemical properties have proved stronger current response after modification. In compassion to the unmodified GF, the FMBO/AC/CB modified GF (FMBO-GF) has wider pH range and higher CIP removal efficiency due to its unique nanoparticles structure. The CIP removal efficiency achieved 95.40% in 30 min, and the removal efficiency of total organic carbon (TOC) achieved 93.77% in 2 h when conditions were optimal (25 mg/L initial CIP concentration, 2 mA/cm 2 current density, FMBO/AC: CB: PTFE of 1:1:5, and 7 initial pH value) in this study. The results of great degradation and mineralization of CIP in this study indicate that the FMBO-GF cathode has huge potential on antibiotics removals in neutral environment.

CAS / MDL: 85721-33-1
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Bioactive Materials · 2021 · IF 14.593

Osteogenic and anti-tumor Cu and Mn-doped borosilicate nanoparticles for syncretic bone repair and chemodynamic therapy in bone tumor treatment

Libin Pang,Renliang Zhao,Jing Chen,Jingxin Ding,Xiaochen Chen,Wenwen Chai,Xu Cui,Xiaolin Li,Deping Wang,Haobo Pan

Critical bone defects caused by extensive excision of malignant bone tumor and the probability of tumor recurrence due to residual tumor cells make malignant bone tumor treatment a major clinical challenge. The present therapeutic strategy concentrates on implanting bone substitutes for defect filling but suffers from failures in both enhancing bone regeneration and inhibiting the growth of tumor cells. Herein, Cu and Mn-doped borosilicate nanoparticles (BSNs) were developed for syncretic bone repairing and anti-tumor treatment, which can enhance bone regeneration through the osteogenic effects of Cu 2+ and Mn 3+ ions and meanwhile induce tumor cells apoptosis through the hydroxyl radicals produced by the Fenton-like reactions of Cu 2+ and Mn 3+ ions. In vitro study showed that both osteogenic differentiation of BMSCs and angiogenesis of endothelial cells were promoted by BSNs, and consistently the critical bone defects of rats were efficiently repaired by BSNs through in vivo evaluation. Meanwhile, BSNs could generate hydroxyl radicals through Fenton-like reactions in the simulated tumor microenvironment, promote the generation of intracellular reactive oxygen species, and eventually induce tumor cell apoptosis. Besides, subcutaneous tumors of mice were effectively inhibited by BSNs without causing toxic side effects to normal tissues and organs. Altogether, Cu and Mn-doped BSNs developed in this work performed dual functions of enhancing osteogenesis and angiogenesis for bone regeneration, and inhibiting tumor growth for chemodynamic therapy, thus holding a great potential for syncretic bone repairing and anti-tumor therapy.

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CRYSTENGCOMM · 2021 ·Vol. 23 ·期 39 ·6899-6908 · IF 3.545

Growth of MSe semiconductor nanowires on metal substrates through an Ag2Se-catalyzed solution–solid–solid mechanism (M = Zn, Cd and Mn)

Huimin Wang,Tingting Wang,Zibin Huang,Yizhuo Liu,Dehui Leng,Junli Wang

The growth of metal chalcogenide nanowires (NWs) on metal substrates is challenging work since the direct reactions taking place between the chalcogen (S, Se or Te) and zero-valent metal (M0) are frequently unable to regulate the crystallization of nanocrystals in an anisotropic one-dimensional (1D) manner. We here report the use of Ag2Se seeds as catalyst particles to realize the growth of metal selenide (MSe) NWs on their respective metal foil or flakes, including ZnSe/Zn, CdSe/Cd, and MnSe/Mn material systems. Metal foil or flakes (M = Zn, Cd and Mn) serve as a support substrate as well as a metal cation source during the NW synthesis. The preformed Ag2Se seeds play the roles of not only catalytic particles that initiate a so-called solution–solid–solid process to produce crystalline MSe NWs on metal substrates, but also inert impurities that promote an electrochemical anodic reaction of the metal to supply metal cations (M0 − 2e → M2+) for the NW formation. The microstructural studies by HRTEM reveal the polytypism and particularly the diameter-dependence of crystal phases and growth directions in the resulting MSe NWs, which can be rationalized from the viewpoints of the energetics and the catalyst/NW interfacial structures. These semiconductor NWs grown on metal foil or flakes may find wide use in photoelectric catalysis and devices without a transfer process of free-standing NWs onto a conductive support substrate.

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Nanomaterials · 2020 ·Vol. 10 ·期 9 ·1629 · IF 4.324

Effects of Carbon Content and Current Density on the Li+ Storage Performance for MnO@C Nanocomposite Derived from Mn-Based Complexes

Ranran Jiao,Li Zhao,Shuli Zhou,Yanjun Zhai,Denghu Wei,Suyuan Zeng,Xianxi Zhang

In this study, a simple method was adopted for the synthesis of MnO@C nanocomposites by combining in-situ reduction and carbonization of the Mn3O4precursor. The carbon content, which was controlled by altering the annealing time in the C2H2/Ar atmosphere, was proved to have great influences on the electrochemical performances of the samples. The relationships between the carbon contents and electrochemical performances of the samples were systematically investigated using the cyclic voltammetry (CV) as well as the electrochemical impedance spectroscopy (EIS) method. The results clearly indicated that the carbon content could influence the electrochemical performances of the samples by altering the Li+diffusion rate, electrical conductivity, polarization, and the electrochemical mechanism. When being used as the anode materials in lithium-ion batteries, the capacity retention rate of the resulting MnO@C after 300 cycles could reach 94% (593 mAh g−1, the specific energy of 182 mWh g−1) under a current density of 1.0 A g−1(1.32 C charge/discharge rate). Meanwhile, this method could be easily scaled up, making the rational design and large-scale application of MnO@C possible.Keywords:MnO@C nanocomposites;carbon content;current density;lithium-ion battery;transition metal oxide anode

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