摘要:
Metal single-atom catalysts offer the dual advantages of high electrochemical activity and near 100 % metal atom utilization, leading to their potential use in low-cost electrochemical sensor development. Herein, a novel electrocatalyst comprising atomically-dispersed Mn on B,N co-doped bamboo-derived carbon (MnSAs-BN-BC) was synthesized via a facile pyrolysis procedure. A high dispersion of Mn single atoms in MnSAs-BN-BC was confirmed by aberration-corrected transmission electron microscopy and elemental mapping. The Mn loading in the MnSAs-BN-BC determined by inductively coupled plasma mass spectrometry was 255 mg kg-1. MnSAs-BNBC displayed outstanding electrocatalytic performance for levodopa (LD) oxidation, allowing a robust electrochemical sensing platform for LD detection to be established. The MnSAs-BN-BC/GCE sensing platform offered a wide LD detection range (concentrations from 2 to 683 mu M) and a very low limit of detection (LOD) of 0.45 mu M, outperforming almost all electrochemical sensors reported to date for LD sensing. The MnSAs-BN-BC/GCE platform also featured outstanding repeatability, reproducibility, selectivity, and stability. The as-developed sensing platform was successfully applied to LD quantification in commercial tablets with satisfactory recoveries (85.2-102.4 %), with the analytical precision of method validated against a traditional UV-vis spectrophotometry method. Density functional theory (DFT) calculations showed that Mn single atom sites lowered the reaction energy barrier for LD oxidation, with the favorable d-band center position of Mn single atom sites in MnSAs-BN-BC contributing to the enhanced LD sensing performance. This work encourages the use of singleatom metal catalysts in design of high-performance electrochemical sensors for the rapid detection of LD.
作者机构:
[Liu, Qin; He, Yingjian; Liu, Jinlong; Qian, Dong; Chen, Xiangxiong; Wang, Bowen; Luo, Ziyu; Liu, JL; Zhang, Xinxin] Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Peoples R China.;[Chen, Xiangxiong] Yoening Tianci Min Changsha Technol Ctr, Changsha 410083, Peoples R China.;[V. Kennedy, John] GNS Sci, Natl Isotope Ctr, POB 30368, Lower Hutt 5010, New Zealand.;[Li, Junhua] Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.;[Waterhouse, Geoffrey I. N.; Waterhouse, GIN] Univ Auckland, Sch Chem Sci, Auckland 1142, New Zealand.
通讯机构:
[Qian, D; Liu, JL ] C;[Waterhouse, GIN ] U;Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Peoples R China.;Univ Auckland, Sch Chem Sci, Auckland 1142, New Zealand.
关键词:
Electrochemical reconstruction;CoMoO4-based catalyst;Phosphorization;Heterojunction;Overall water splitting
摘要:
Phosphorization of molybdates has been shown to promote hydrogen evolution reaction (HER) activity but is usually detrimental to oxygen evolution reaction (OER) activity, frustrating efforts to create bifunctional HER/OER electrocatalysts. Herein, we show that Fe2O3-modulated P-doped CoMoO4 on nickel foam (Fe-P-CMO) is an excellent bifunctional HER/OER electrocatalyst in alkaline media, with the adverse effect of phosphorization on the OER activity of CoMoO4 being countered via Fe2O3 introduction. An alkaline splitting electrolyser assembled directly using the self-supporting Fe-P-CMO electrode possessed outstanding long-term durability with ultralow cell voltages of 1.48 and 1.59 V required to achieve current densities of 10 and 100 mA cm−2, respectively. Detailed experimental investigations showed that during HER, P-doped CoMoO4 in Fe-P-CMO underwent surface reconstruction with the in-situ formation of Co(OH)2 on the P-CoMoO4 (Co(OH)2/P-CoMoO4). During OER, P-doped CoMoO4 was deeply reconstructed to CoOOH with the complete dissolution of Mo, leading to the in-situ formation of Fe2O3/CoOOH heterojunctions.
作者机构:
[Wu, Yi-jin; Wang, Si-ping; Liu, Wan-xin; Zhou, Xiao; Wu, YJ; Li, Yi; Tan, Liang] Hengyang Normal Univ, Coll Chem & Mat Sci, Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421001, Peoples R China.;[Zhou, Yao; Zhou, Y] Xiamen Univ, Coll Energy, Xiamen 361005, Peoples R China.;[Tu, Teng-xiu] Chinese Acad Sci, Inst Solid State Phys, Hefei Inst Phys Sci, Hefei 230031, Peoples R China.;[Zhang, Peng-fang] Liaocheng Univ, Sch Chem & Chem Engn, Shandong Prov Key Lab Chem Energy Storage & Novel, Liaocheng 252000, Peoples R China.
通讯机构:
[Wu, YJ ] H;[Zhou, Y ] X;Hengyang Normal Univ, Coll Chem & Mat Sci, Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421001, Peoples R China.;Xiamen Univ, Coll Energy, Xiamen 361005, Peoples R China.
摘要:
Different from the conventional Zinc-Air batteries which only involves oxygen reduction and evolution (ORR/ OER) in the cathode, the cathode of rechargeable zinc-air/iodide hybrid batteries (ZAIHBs), with the addition of I- species, involves I- electrooxidation (IOR) during charging and oxygen/iodate reduction (ORR and IDR) during discharging. This work reports the synthesis of a hierarchically porous tungsten-based nitrogen-doped carbon framework (W/N/C) with abundant WNx active sites and numerous ultrafine WN nanoclusters and explores their application as a trifunctional IOR/ORR/IDR electrocatalyst for ZAIHBs. The formation mechanism of ZIF-8-derived W/N/C framework as well as its structural and compositional features were investigated. The catalyst demonstrates high trifunctional catalytic activity and robust durability towards IOR/ORR/IDR in alkaline condition, owing to the uniform copresence of the numerous sub-nanometer-sized WN nanoclusters and the abundant single atom WNx sites in the hierarchically structured carbon framework. When applied in homemade ZAIHBs, it revealed a high peak energy density (141.9 mW cm-2) and remarkable cycling stability (65 h), outperforming the commercial Pt/C catalysts. This work demonstrates the multi-functional electrocatalytic activity of tungsten-based non-noble metal electrocatalyst for high-performance ZAIHBs.
摘要:
Phosphorus is widely used in agriculture and industry. However, excessive phosphorus can cause eutrophication in aquatic environment. Therefore, the development of an simple, efficient and economical method for phos-phate removal from wastewater is urgently needed. In this study, calcium aluminum layered double hydroxides (CaAl-LDHs) and six amino acid intercalated calcium aluminum layered double hydroxides (CaAl-amino acid-LDHs) was prepared by a facile method. In order to identify optimal amino acid, the adsorption performance of phosphate for six CaAl-amino acid-LDHs were comparatively studied. A high phosphate adsorption capacity were observed for L-Aspartic acid intercalated calcium aluminum layered double hydroxides (CaAl-Asp-LDHs). Experimental results showed that CaAl-Asp-LDHs can achieve phosphate anion adsorption capacity of 569.95 mg/g, which is significantly higher than that of CaAl-LDHs (236.86 mg/g) at pH 6.0 and favorable selectivity was observed when compared with other common anions. CaAl-Asp-LDHs exhibited a faster phosphate removal than that of CaAl-LDHs. The adsorption data of aqueous phosphate anion using CaAl-LDHs and CaAl-Asp-LDHs could be well described by the Langmuir isotherm model and pseudo-second order kinetics. Furthermore, based on the structural and morphological features, as well as fourier transform infrared spectrometer (FT-IR), diffraction of x-rays (XRD), x-ray photoelectron spectroscopy (XPS), scanning electron microscope with energy dispersive x-ray spectroscopy (SEM-EDS) and element mapping, the phosphate adsorption mechanism on CaAl-Asp-LDHs involved the electrostatic attraction, hydrogen bonds, complexation and ion exchange. Compared with the performance of other phosphate sorbents in other reported, CaAl-Asp-LDHs has the highest adsorption value. The synthesized CaAl-Asp-LDHs, therefore, would be a promising environmentally friendly material for the efficient removal of phosphate from aquatic environments.
期刊:
Chemical Engineering Science,2024年285:119575 ISSN:0009-2509
通讯作者:
Liu, J
作者机构:
[Liu, Jian; Liu, Yuanyuan; Ni, Wenjin; Yi, Zhengji] Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.;[Liu, Jian; Yi, Zhengji] Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Peoples R China.;[Liu, Jian; Yi, Zhengji] Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Hengyang 421008, Peoples R China.;[Ni, Wenjin] Xiangtan Univ, Sch Chem Engn, Xiangtan 411105, Peoples R China.
通讯机构:
[Liu, J ] H;Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.
关键词:
Dandelion-like;Nickel foam;PMS;Fixed bed
摘要:
A novel dandelion-like catalyst, nickel foam supported NiCo2O4 (NiCo2O4/NF), was successfully synthesized and applied to the activation of peroxymonosulfate (PMS) in a fixed bed system for the degradation of Orange II (OII). The physicochemical properties of synthesis catalysts were identified by various characterization methods (SEM, EDS, XRD and XPS), revealing that the dandelion-like NiCo2O4 nanosheets were evenly distributed on the surface of NF. NiCo2O4/NF-250 showed excellent catalytic performance at a hydrothermal reaction time of 8 h, urea/ metal ratio of 10:1, and Co/Ni concentration of 10 mM/5 mM. When PMS concentration was 5 mM, reaction temperature was 50 celcius, pH was 7.5, space velocity was 0.236 min-1, the conversion ratios of OII, PMS and COD were 99.8 %, 71.3 %, and 71.4 % at 240 min, respectively. In particular, NiCo2O4/NF still could reach 99.9 % OII conversion and 64.4 % COD conversion in the third cycle. DFT calculations implied that NiCo2O4/NF had excellent PMS activation performance.
期刊:
Chemical Engineering Journal,2024年483 ISSN:1385-8947
通讯作者:
Xia, Xiaohong;Li, R;Xia, XH
作者机构:
[Gao, Yingxv; Chen, Yuxi; Li, R; Hui, Qunbo; Xia, Xiaohong; Li, Run; Xia, XH; Liu, Hongbo; Liu, Qi] Hunan Univ, Coll Mat Sci & Engn, Changsha 410082, Hunan, Peoples R China.;[Xia, Xiaohong; Xia, XH] Hunan Univ, Hunan Joint Int Lab Adv Mat & Technol Clean Energy, Changsha 410082, Hunan, Peoples R China.;[Wang, Deping] Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.
通讯机构:
[Li, R ; Xia, XH; Xia, XH ] H;Hunan Univ, Coll Mat Sci & Engn, Changsha 410082, Hunan, Peoples R China.;Hunan Univ, Hunan Joint Int Lab Adv Mat & Technol Clean Energy, Changsha 410082, Hunan, Peoples R China.
关键词:
Conjugated microporous polymers;Nitrogen and sulfur coordination;Anode materials;Potassium-ion batteries
摘要:
Conjugated microporous polymers (CMPs) with enhanced electrical conductivity and insolubility against liquid electrolytes are receiving increasing attention as promising organic anode materials for rechargeable batteries. However, the poor electronic conductivity and restricted-access active sites limit the specific capacity and cycling stability of CMPs and the potassium-storage mechanism in hetero-incorporated CMPs not well understood. Herein, a highly conjugated polymer network with hierarchically interconnected porous structure was deliberately constructed by selecting 4,7-dibromo-2,1,3-benzothiadiazole (BT) and 1,3,5-triacetylene benzene as the acceptor and donor, respectively. The good planarity and high pi-electron delocalization of BT units lead to an enhanced conductivity of BT-CMP. Ex-XPS analysis and DFT calculations reveal that the synergistic coupling of S and N enables a prompt complexation and release of K+ ions and improves the coordination activity of the C--N active sites. More importantly, the hierarchically interconnected porous networks make active sites facilely accessible and accommodate the volumetric expansion effectively, enabling highly stable storage of K-ions. Therefore, the as-prepared BT-CMP anode displays a high specific capacity (462 mAh/g- 1 at 30 mA g-1 after 100 cycles) and ultra-long stability (226.2 mAh g-1 at 1000 mA g-1 after 2000 cycles without significant attenuation) in potassium-ion storage.
摘要:
Six aroylhydrazone di-m-chlorobenzyltin complexes {[X-C(6)H(4)(O)C=N-N=C(Me)COO](MeOH)(m-Cl-C(6)H(4)CH(2))(2)Sn}(2) (X = p-Me- (1), p-MeO- (2), p-t-Bu- (3), p-NO(2)- (4), p-OH- (5) or o-OH- (6)) were synthesized and characterized by HRMS (high-resolution mass spectrometry), NMR (nuclear magnetic resonance spectroscopy), IR (Fourier transform infrared spectroscopy), and TGA (thermogravimetric analysis) techniques. The molecular structure of complexes 1-6 was confirmed by single-crystal X-ray crystallography. The structure of complexes showed a distorted pentagonal bipyramidal configuration around the tin atom center, and the ligands adopted a tridentate chelating mode. Fascinatingly, either one-dimensional infinite chain structures or two-dimensional network structures were observed in the complexes through hydrogen bonds. Complex 2 has the strongest inhibitory effect on MCF7 and HepG2 cell proliferation, its effect was superior to that of the positive control drug cisplatin. The interaction of ct-DNA (calf-thymus DNA) with complex 2 was explored using UV absorption (ultraviolet absorption) and fluorescence spectroscopy. Complex 2 exhibited a moderate affinity for ct-DNA through intercalation modes. The interaction of complex 2 with ct-DNA has also been supported by molecular docking studies.
作者机构:
[Hu, JW; Zhai, Yunran; Cui, Ying; Hu, Jiawen] Hunan Univ, Coll Chem & Chem Engn, Adv Catalyt Engn Res Ctr, Hunan Key Lab Two Dimens Mat,Minist Educ, Changsha 410082, Peoples R China.;[Cui, Ying; Li, Junhua] Hengyang Normal Univ, Coll Chem & Mat Sci, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421001, Peoples R China.;[Fan, Shanji; Liu, Yingjie] Univ South China, Affiliated Hosp 1, Hengyang Med Sch, Dept Breast & Thyroid Surg, Hengyang 421000, Peoples R China.;[Wang, Lijia] Zhejiang Univ, Natl Clin Res Ctr Child Hlth, Natl Childrens Reg Med Ctr, Childrens Hosp,Sch Med, Hangzhou 310052, Zhejiang, Peoples R China.
通讯机构:
[Hu, JW ] H;[Wang, LJ ] Z;Hunan Univ, Coll Chem & Chem Engn, Adv Catalyt Engn Res Ctr, Hunan Key Lab Two Dimens Mat,Minist Educ, Changsha 410082, Peoples R China.;Zhejiang Univ, Natl Clin Res Ctr Child Hlth, Natl Childrens Reg Med Ctr, Childrens Hosp,Sch Med, Hangzhou 310052, Zhejiang, Peoples R China.
摘要:
This study reports a metal-enhanced fluorescence chemodosimeter for highly sensitive detection of Hg2+ ions. Silica-coated Au nanoparticles (Au@SiO2 NPs) with a pinhole-free 4-5 nm shell were synthesized and functionalized with a monolayer of turn-on fluorescent probes. Compared to other organic fluorescent probes suffering from poor biocompatibility and detection limits, this design of a monolayer of turn-on fluorescent probes immobilized on the Au@SiO2 NPs with a pinhole-free 4-5 nm shell avoids fluorescence quenching and allows the fluorescent probe within the field of the inner Au NPs to experience metal-enhanced fluorescence. With this design, the chemodosimeter permits fluorescence emission in the presence of Hg2+ ions, because they trigger the ring-opening reaction of the fluorescent probe immobilized on the Au@SiO2 NPs. Additionally, the fluorescent probe is distanced by the thin SiO2 shell from directly attaching to the metallic Au NPs, which not only avoids fluorescence quenching but allows the fluorescent probe within the long-ranged field of the inner Au NPs to experience metal-enhanced fluorescence. As a result, the detection limit for the chemodosimeter can reach up to 5.0 x 10(-11) M, nearly two orders of magnitude higher than that achieved for the free fluorescent probe. We also demonstrate the acquisition of images of Hg2+ in HTC116 cells and zebrafish using a simple fluorescence confocal imaging technique. The fluorescence response results for HTC116 cells and zebrafish show that the probes can permeate into cells and organisms. Considering the availability of the many organic fluorescent probes that have been designed, the current designed metal-enhanced fluorescence chemodosimeter holds great potential for fluorescence detection of diverse species and fluorescence imaging.
期刊:
JOURNAL OF ORGANIC CHEMISTRY,2024年89(5):2939-2950 ISSN:0022-3263
通讯作者:
Fu, Yang;Ding, QP
作者机构:
[Tan, Yuxing; Ding, Qiuping; Jiang, Wu-jiu; Fu, Yang; Ding, QP] Jiangxi Normal Univ, Key Lab Green Chem Jiangxi Prov, Key Lab Fluorine & Silicon Energy Mat & Chem, Minist Educ, Nanchang 330022, Jiangxi, Peoples R China.;[Tan, Yuxing; Jiang, Wu-jiu; Ni, Penghui] Hengyang Normal Univ, Coll Chem & Mat Sci, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Hunan, Peoples R China.
通讯机构:
[Fu, Y; Ding, QP ] J;Jiangxi Normal Univ, Key Lab Green Chem Jiangxi Prov, Key Lab Fluorine & Silicon Energy Mat & Chem, Minist Educ, Nanchang 330022, Jiangxi, Peoples R China.
摘要:
Herein, we developed a highly selective, efficient, and simple method for direct transamidation of thioamides with amines, promoted by commercially available acetophenone under metal-/solvent-free conditions. The reaction tolerated a wide range of functional groups and substrates, including single- or double-thioamides, benzylamines, or alkyl/cycloalkyl-substituted aliphatic amines. The present protocol can be applied to gram-scale in good yields. In addition, the Pt-/Ni-complexes of double-transamidation products were obtained in good to excellent yields. The investigation of photophysical properties indicated that the fluorescence spectra of Pt-complexes showed an emission band centered at 550-750 nm and exhibited red fluorescence when irradiated by a UV lamp (365 nm).
作者机构:
[Xu, Zhuo-Wen; Xia, Yu-Xuan; Li, Wei; Liu, Yang; Li, W] Hengyang Normal Univ, Dept Chem & Mat Sci, Hengyang 421008, Hunan, Peoples R China.;[Li, Chang-Hong] Hunan Inst Technol, Dept Chem Engn, Hengyang 421002, Hunan, Peoples R China.
通讯机构:
[Liu, Y ; Li, W] H;Hengyang Normal Univ, Dept Chem & Mat Sci, Hengyang 421008, Hunan, Peoples R China.
摘要:
C75H76N10O23Tb2, triclinic, P - (1) over bar (no. 2), a = 10.4524(13) angstrom, b = 12.9626(16) angstrom, c = 15.2003(18) angstrom, alpha = 108.674(2)degrees, beta = 94.931(2)degrees, gamma = 101.617(2)degrees, V = 1885.8(4) nm(3), Z = 1, R (gt) (F) = 0.0236, wR (ref) (F-2) = 0.0584, T = 296 K.
期刊:
Journal of the European Ceramic Society,2024年44(6):3747-3759 ISSN:0955-2219
通讯作者:
Sun, Junbin;Lu, WH
作者机构:
[Liu, Zhihua; Sun, Junbin; Lu, Weihong; Sun, JB; Ou, Jiani; Bin, Xing; Lu, WH] Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.;[Sun, Junbin; Lu, Weihong] Hengyang Normal Univ, Hunan Prov Key Lab Funct Met Organ Cpds, Hengyang 421008, Peoples R China.;[Sun, Junbin; Lu, Weihong] Hengyang Normal Univ, Coll Hunan Prov, Key Lab Organometall New Mat, Hengyang 421008, Peoples R China.;[Sun, Junbin; Lu, Weihong] Hengyang Normal Univ, Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Hengyang 421008, Peoples R China.
通讯机构:
[Sun, JB; Lu, WH ] H;Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.
关键词:
CeO2;CMAS corrosion
摘要:
Alumina based ceramic materials, such as LaMgAl11O19 (LMA) containing amounts of Al, usually resist the CMAS corrosion through forming a compact layer of the CaAl2Si2O8. In this work, the LMA/CeO2 mixed powders in mole ratios of 5:5 (L5C5), 7:3 (L7C3) and 9:1 (L9C1) were pressed and sintered to prepare the ceramic bulks. The resistance to CMAS corrosion of the LMA/CeO2, the CeO2 and the LMA ceramic bulks were tested and compared at 1250 degrees C and 1350 degrees C for 1 h, 5 h and 10 h. Results showed that the added CeO2 in the LMA can decrease the porosity and improve the resistance to CMAS corrosion. The combined effects of the LMA and CeO2 promoted the formation of the CaAl2Si2O8. The L5C5 and the L9C1 with appropriate composition have good resistance to CMAS corrosion at 1250 degrees C, and the L9C1 can alleviate CMAS infiltration compared with the LMA and other proportional materials at 1350 degrees C.
摘要:
Developing novel photoelectric functional materials based on dithienylethenes (DTEs) building block has drawn increasing attention due to their excellent photochromic properties. In this contribution, two D-A type DTE derivatives 3 and 4 bearing triphenylamine (TPA) and anthraquinone (or anthracene) groups have been synthesized, and their structures have been characterized by means of NMR and MS. The UV-vis spectroscopy results show that compounds 3 and 4 exhibited reversible photochromism in toluene and THF solutions under UV/vis light irradiation, featuring good fatigue resistance and responsiveness. However, almost no photochromic properties for DTEs 3 and 4 were observed in larger polar DMSO. Interestingly, DTE 3 with obvious push-pull characteristics also displayed visible-light driven photochromic behavior in toluene. Meanwhile, fluorescence spectroscopy experiments have shown that DTE 4 with the anthracene fluorescent group showed fluorescent switching properties upon UV/vis light irradiation in toluene and THF solutions. The electrochemical results revealed a certain decrease in the half-wave potential of TPA-based 3 and 4 after UV irradiation, suggesting that the increasing conjugation degree of the ring-closed isomers results in the increase of HOMO orbital energy and the decrease of HOMO-LUMO gap and is beneficial for the occurrence of oxidation process, which are further proved by DFT calculations. TDDFT predicts that the transition absorption of the ring-closed isomers 3c and 4c respectively at 615 nm and 651 nm mainly come from pi-pi* mixed with TPA-*anthraquinone CT or TPA-*anthracene CT transition, which is consistent with the experimental results.
通讯机构:
[Yun-Wu Li; Jin-Sheng Zhao] S;[Yi-Jin Wu] K;Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, and School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252000, P. R. China<&wdkj&>Key Laboratory of Functional Metal-Organic Compounds of Hunan Province, Hunan Province Universities Key Laboratory of Functional Organometallic Materials, College of Chemistry and Material Science, Hengyang Normal University, Hengyang 421008, P. R. China
摘要:
The cathodic product Li(2)CO(3), due to its high decomposition potential, has hindered the practical application of rechargeable Li-CO(2)/O(2) batteries. To overcome this bottleneck, a Pt/FeNC cathodic catalyst is fabricated by dispersing Pt nanoparticles (NPs) with a uniform size of 2.4 nm and 8.3 wt % loading amount into a porous microcube FeNC support for high-performance rechargeable Li-CO(2)/O(2) batteries. The FeNC matrix is composed of numerous two-dimensional (2D) carbon nanosheets, which is derived from an Fe-doping zinc metal-organic framework (Zn-MOF). Importantly, using Pt/FeNC as the cathodic catalyst, the Li-CO(2)/O(2) (V(CO(2))/V(O(2)) = 4:1) battery displays the lowest overpotential of 0.54 V and a long-term stability of 142 cycles, which is superior to batteries with FeNC (1.67 V, 47 cycles) and NC (1.87 V, 23 cycles) catalysts. The FeNC matrix and Pt NPs can exert a synergetic effect to decrease the decomposition potential of Li(2)CO(3) and thus enhance the battery performance. In situ Fourier transform infrared (FTIR) spectroscopy further confirms that Li(2)CO(3) can be completely decomposed under a low potential of 3.3 V using the Pt/FeNC catalyst. Impressively, Li(2)CO(3) exhibits a film structure on the surface of the Pt/FeNC catalysts by scanning electron microscopy (SEM), and its size can be limited by the confined space between the carbon sheets in Pt/FeNC, which enlarges the better contacting interface. In addition, density functional theory (DFT) calculations reveal that the Pt and FeNC catalysts show a higher adsorption energy for Li(2)CO(3) and Li(2)CO(4) intermediates compared to the NC catalyst, and the possible discharge pathways are deeply investigated. The synergetic effect between the FeNC support and Pt active sites makes the Li-CO(2)/O(2) battery achieve optimal performance.
作者机构:
[Tan, L.; Wu, Y. -j.; Tan, L; Huang, Z. -x.; Liu, H.; Liu, Y. -x.; Wu, YJ] Hengyang Normal Univ, Coll Chem & Mat Sci, Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421001, Peoples R China.
通讯机构:
[Tan, L; Wu, YJ ] H;Hengyang Normal Univ, Coll Chem & Mat Sci, Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421001, Peoples R China.
关键词:
Ag coating;Surfactant;Zinc-metal battery;Zinc dendrite
摘要:
Rechargeable aqueous zinc (Zn) batteries are promising for large energy storage due to their low cost, high safety, and environmental compatibility, but their commercialization is hindered by the severe irreversibility of Zn metal anodes as exemplified by water-induced side reactions (H2 evolution and Zn corrosion) and dendrite growth. In this work, hierarchical layered silver-coated zinc anode under the assistance of anionic surfactant (trisodium citrate) was prepared for long-time cycle stabilities of zinc stripping and plating, where Ag coating has a strong affinity to Zn adatoms and hierarchical structure exhibits a positive role in inducing the (002) plane preferred-orientation growth of Zn phase. Benefiting from these features, hierarchical Ag-coated zinc anode was able to operate stability for more than 1200 cycles compared with the pure zinc anode at 2 mA/cm(2) for 1 mAh/cm(2), and an asymmetric cell shows superior Coulombic efficiency of similar to 99.6% over 800 cycles at a current density of 1 mA/cm(2) and 0.5 mAh/ cm(2), as well as a long cycling stability of 500 cycles with capacity of 115 mAh/g in MnO2||H-Zn@Ag full batteries. This work provides a new insight to improve the performance of Zn-metal batteries.(c) 2023 Elsevier Ltd. All rights reserved.
期刊:
Journal of Physical Chemistry Letters,2023年14(26):6099-6109 ISSN:1948-7185
通讯作者:
Qian, Dong;Liu, JL;Waterhouse, GIN
作者机构:
[Liu, Jinlong; Qian, Dong; Chen, Xiangxiong; Wang, Bowen; Luo, Ziyu; Li, Jie; Liu, JL; Zhang, Xinxin; Liu, Canhui] Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Peoples R China.;[Chen, Xiangxiong] Yoening Tianci Min Changsha Technol Ctr, Changsha 410083, Peoples R China.;[Li, Junhua] Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.;[Waterhouse, Geoffrey I. N.; Waterhouse, GIN] Univ Auckland, Sch Chem Sci, Auckland 1142, New Zealand.
通讯机构:
[Qian, D; Liu, JL ] C;[Waterhouse, GIN ] U;Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Peoples R China.;Univ Auckland, Sch Chem Sci, Auckland 1142, New Zealand.
摘要:
Herein, a simple two-step synthetic method was developed for the synthesis of NiFe(2)O(4) nano-microrods supported on Ketjenblack carbon (NiFe(2)O(4)/KB). A sodium tartrate-assisted hydrothermal method was employed for the synthesis of a NiFe-MOF/KB precursor, which was then pyrolyzed under N(2) at 500 °C to yield NiFe(2)O(4)/KB. Benefiting from the presence of high-valence Ni(3+) and Fe(3+), high conductivity, and a large electrochemically active surface area, NiFe(2)O(4)/KB delivered outstanding OER electrocatalytic performance under alkaline conditions, including a very low overpotential of 258 mV (vs RHE) at 10 mA cm(-2), a small Tafel slope of 43.01 mV dec(-1), and excellent durability in 1.0 M KOH. Density functional theory calculations verified the superior alkaline OER electrocatalytic activity of NiFe(2)O(4) to IrO(2). While both catalysts possessed a similar metallic ground state, NiFe(2)O(4) offered a lower energy barrier in the rate-determining OER step (*OOH → O(2)) compared to IrO(2), resulting in faster OER kinetics.
摘要:
In recent years, carbon-based materials catalyzing peroxymonosulfate (PMS) for green degradation of persistent or-ganic pollutants have attracted increasing attention. However, PMS activation by hydrochar composite (e.g. hydrochar-montomorillonite) has rarely been investigated. Herein, a simple preparation, low-cost and eco-friendly catalyst of hydrochar-montmorillonite composite (HC-Mt) was prepared to firstly catalyze PMS for the degradation of dicamba (DIC). The as-prepared HC-Mt showed a remarkably better catalyzing performance for PMS than pure hydrochar (HC) due to its good physicochemical characteristics and abundant oxygen-containing groups. Further-more, the electron spin resonance (ESR) and quenching tests revealed that active species such as SO4 center dot-, center dot OH and O2 center dot- all participated in the degradation process. DIC sites on C6, Cl 10, and O15 exhibited higher reactivity according to the density functional theory (DFT) calculation, which were easily attacked by active species. The DIC degradation mainly occurred via hydroxyl substitution, decarboxylation, oxidation and ring-cleavage and finally most of the inter-mediates were mineralized into CO2 and H2O. Finally, the phytotoxicity assessment was measured by the germination growth situation of tobacco and mung beans in the presence of DIC (with or without treatment by HC-Mt/PMS). The result showed that HC-Mt/PMS could significantly reduce the phytotoxicity of DIC to crops, suggesting that catalyzing PMS using HC-Mt was environmentally friendly. Therefore, this work did not only provide a novel catalyzing PMS strategy using hydrochar composite for wastewater treatment, but also give a new idea for herbicide phytotoxicity management.