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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2022 · IF 5.518

Facile hydrothermal synthesis of co-glycerate as an efficient peroxymonosulfate activator for rhodamine B degradation

Qin Yang,Yujie Zhang,Jie Liang,Yongsong Luo,Qian Liu,Yingchun Yang,Xuping Sun

Sulfate radical based advanced oxidation processes (SR-AOPs) are regarded as a promising technology to degrade organic pollutants in water. Here, hydrothermally synthesized Co-glycerate (Co-G) microspheres are proposed as an efficient heterogeneous catalyst to activate peroxymonosulfate (PMS) for degradation of refractory organic pollutant rhodamine B (RhB) in aqueous solution. The presence of Co-G microspheres enhanced the degradation rate significantly with a short full degradation time (8 min) and a total organic carbon (TOC) removal exceeding 41% (10 min), thus implying the excellent catalytic performance of Co-G microspheres for PMS activation. Furthermore, the effects of PMS and catalyst concentration, initial pH value and co-existing ions on RhB degradation were investigated. Radical quenching and EPR tests identify that active species including SO 4 - ·, HO·, O 2 - · and 1 O 2 are involved in the degradation process. Additionally, a possible reaction mechanism of PMS activation by Co-G microspheres for RhB degradation was suggested. This study can provide a new insight for design of cobalt-based heterogeneous catalysts as activators to activation PMS for pollutants degradation.

研究领域: 环境科学 · 化学工程 · 水处理
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JOURNAL OF CONTROLLED RELEASE · 2022 · IF 11.467

Glycoprotein Ib-regulated micro platelet ghost for biosafe distribution and photothermal oncotherapy

Jiahui Zou,Jianhua He,Xiaobo Wang,Yajie Wang,Chenchen Wu,Mengya Shi,Hulin Jiang,Zimei Wu,Jianping Liu,Wenli Zhang

Despite the tremendous theranostics potential of nano-scale drug delivery system (NDDS) in oncology field, their tumor-targeting efficiency and safety remain major challenges due to their proneness of off-target accumulation through widespread vascular endothelial gaps (up to 1 μm). To address this problem, in this research, micro-sized cellular platelet “ghosts” (PGs, 1.32 μm, platelet without inner granules and coagulation) were employed as carriers to ship hollow gold nanoparticles (HGNs, 58.7 nm), forming a hierarchical biosafe system ( [email protected] ) to reduce normal tissue interception and enhance tumor targeting delivery of HGNs for improved photothermal therapy . PGs were prepared by an optimized “swelling-extrusion-elution” method, HGNs were loaded in PGs ( [email protected] ) through a “hypotonic dialysis” method and the safety and biodistribution of the system was evaluated in vitro and in vivo . In in vitro condition that stimulated the tumoral vessel acidic microenvironment (pH = 6.5), [email protected] were demonstrated with enhanced membrane fluidity through down-regulation of the glycoprotein Ib expressed on the PGs. This change induced a burst release of nano-sized HGNs which were capable to traverse vascular endothelium layer on a tumor-endothelial cell transwell model, whilst the micro-sized PG carriers were intercepted. In comparison to nano-sized platelet membrane-coated carriers ( [email protected] ), [email protected] showed enhanced internalization and cytotoxicity to 4T1 cells. In animal models, [email protected] remarkably prolonged circulation most likely due to the presence of “self-recognition” receptor-CD47 of PGs, and effectively reduced normal tissue interception via the micro-scale size effect. These both contributed to the significantly improved tumor targeting efficiency of HGNs. [email protected] generated the greater antitumor photothermal efficacy alongside safety in the animals compared to [email protected] Collectively, this study demonstrated the potential of the micro-scale PGs equipped with adjusted membrane GP Ib as biosafe vehicles for HGNs or possibly other nanodrugs. The statement of significance Despite the tremendous theranostics potentials, the safety and tumor-targeting efficiency of nano-scale drug delivery systems (NDDS) are compromised by their undesirable accumulation in normal tissues with widespread vascular endothelial gaps, such as many tumor-targeted NDDSs still accumulated much in liver and/or spleen. Herein, we explored a micro-nano biomimetic cascade delivery system to address the above drawbacks. By forming a hierarchical biosafe system, micro-sized platelet “ghost” (PGs, 1.32 μm) was employed as tumor-targeted delivery carrier to transport hollow gold nanoparticles (HGNs, 58.7 nm). It was demonstrated that this micro-size system could maintain platelet membrane structure thus prolong in vivo circulation, while avoiding extravasation into normal tissues. [email protected] could sensitively respond to the acidic microenvironment near tumor vessel via down-regulation of glycoprotein Ib and rapidly release “nano-bullets”-HGNs to further penetrate into the tumor tissues through EPR effect , thus enhancing photothermal efficacy generated by HGNs under NIR irradiation. Collectively, the micro-scaled PGs could be biosafe vehicles for improved tumor-targeted delivery of HGNs or possibly other nanodrugs.

CAS / MDL: 16961-25-4 16940-66-2
研究领域: 肿瘤学 · 纳米技术 · 药物递送 · 生物医学工程 · 治疗诊断学
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JOURNAL OF CONTROLLED RELEASE · 2023 · IF 10.8

Platelet-mimicking supramolecular nanomedicine with precisely integrated prodrugs for cascade amplification of synergistic chemotherapy

Yuan-Fu Ding,Ziyi Wang,Cheryl H.T. Kwong,Yonghua Zhao,Greta S.P. Mok,Hua-Zhong Yu,Ruibing Wang

Camptothecin (CPT) and cisplatin (Pt) have shown synergistic effects on a variety of cancers during preclinical and clinical studies. However, the ratio of the two drugs often could not be precisely regulated in different delivery systems, which hinders the desired synergistic effect. In addition, the low delivery efficiency of the two drugs to the tumor further impedes the ideal therapeutic outcomes. Herein, we report that a platelet-mimicking supramolecular nanomedicine (SN) could precisely control of the ratio of CPT and Pt with a high tumor accumulation rate for cascade amplification of synergistic chemotherapy. The SN was fabricated via the host–guest interaction between cucurbit[7]uril conjugated hyaluronic acid (HA-CB[7]) and adamantane (ADA) respectively functionalized CPT- and Pt-based prodrugs . The ratio of CPT and Pt in the SN could be facilely regulated by simply controlling the loading ratio, based on the strong binding affinity between CB[7] and ADA, and SN60 with 60% CPT and 40% Pt showed the highest synergistic effects on 4T1 cells. To improve the tumor accumulation efficiency of SN, 5,6-dimethylxanthenone-4-acetic acid (DMXAA, a tumor vasculature-disruptive agent) was loaded into the optimized SN and then coated with platelet membrane to yield platelet-mimicking supramolecular nanomedicine ( [email protected] ). [email protected] could first passively accumulate in tumors owing to the enhanced permeability and retention (EPR) effect after intravenous administration. The initially release of DMXAA from [email protected] could induce tumor vascular disruption, and the resultant epithelial collagen exposure around the disrupted tumor vasculature provided a target for further recruitment of platelet-mimicking SN, leading to cascade amplification of tumor accumulation with synergistic chemotherapy. Hence, this platelet-mimicking supramolecular nanomedicine presents a universal supramolecular strategy to finely regulate the ratio of loaded pro-drugs, and improve the accumulation efficiency to amplify chemotherapy via platelet-mimics.

研究领域: 纳米医学 · 药学 · 肿瘤学 · 药物递送系统
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CHEMICAL ENGINEERING JOURNAL · 2018 · IF 6.735

Kinetic and mechanistic investigations of the degradation of sulfachloropyridazine in heat-activated persulfate oxidation process

Lin Liu,Sen Lin,Wei Zhang,Usman Farooq,Genxiang Shen,Shuangqing Hu

Sulfachloropyridazine (SCP) has significant threat to natural environment and human health worldwide. Efforts have been made to remove SCP using traditional water treatment technologies but the outputs achieved are limited. In this study, we focused on heat-activated persulfate oxidation of SCP. Various factors have been investigated, such as PS concentration, initial pH, temperature and natural water constituent effects. The results showed that the SCP removal rate constants (k obs ) followed a quadratic relationship with initial persulfate concentrations (k obs  = −1.526 ∗ 10 −6 [PS] 0 2  + 5.621 ∗ 10 −4 [PS] 0  + 0.01158, R 2  = 0.923, [PS] 0  = 17.5–280 µM) and excellent fitting with the Arrhenius equation (ln (k obs ) = −19487.9/T + 59.63, R 2  = 0.967, T = 303.15–323.15 K). The pH tests were applied at a wide range of 3.0–10.0, the quickest degradation rate observed at pH 3.0. The consumption rate of PS was strengthened at elevated temperatures, and 40 °C was determined to be an optimal condition. The presence of chloride (Cl − ), bicarbonate (HCO 3 − ) and humic acid all showed inhibitory effects. The radical scavenging experiments revealed that HO and SO 4 − were predominant oxidizing species responsible for SCP removal. These oxidizing species were further verified by EPR tests. LC-MS/MS analysis confirmed seven kinds of byproducts during the removal process which are mainly deriving from SO 2 extrusion/Smile-type rearrangement and S-N bond cleavage. Efficiencies of the antibiotics removal were over 85% when 50 g L −1  PS was added to piggery anaerobic fermentation slurry. This remediation technology may appear as a promising way for the removal of highly antibiotics-contaminated water in a small scale.

研究领域: 环境科学 · 水处理 · 化学工程 · 分析化学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Mechanical agitation and ultrasound constructed in situ Fenton system: The role of atomic hydrogen for Fe(III) reduction

Huaimin Wang,Shuang Meng,Zixuan Zhang,Chenying Zhou,Heng Zhang,Yang Liu,Chuan-shu He,Peng Zhou,Bo Lai

It has been reported that the ultrasonic agitation coupled system (US/A) has higher oxidation efficiency than the pure ultrasonic system (US), and the atomic hydrogen ( H) and hydroxyl radicals ( OH) produced by H 2 O cracking and in situ hydrogen peroxide (H 2 O 2 ) can be significantly detected. In order to utilize the residual H 2 O 2 and explore the role and fate of H, US/A/Fe(III) as an in situ Fenton oxidation system, was constructed in this study. The experimental results proved that the system can generate H 2 O 2 in situ , and adding Fe(III) could significantly promote the oxidation of refractory organic pollutants. Quenching tests, probes experiments and EPR test were performed to successfully monitor the existence of OH. The contribution of H to Fe(III) reduction was speculated and confirmed. In addition, the kinetic model showed the decomposition rate of water molecule and the reduction rate of Fe(III) by H under different ultrasonic power. The effects of the factors (pH, coexisting substance, and actual water environment) on degrading organic pollutants were evaluated. Therefore, this work provides new strategy and mechanistic insight into in situ Fenton technique by coupling ultrasonic agitation and Fe(III) without external oxidants.

研究领域: 环境科学 · 化学工程 · 水处理 · 高级氧化过程
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ACS Nano · 2021 · IF 15.881

One-Step Integration of Tumor Microenvironment-Responsive Calcium and Copper Peroxides Nanocomposite for Enhanced Chemodynamic/Ion-Interference Therapy

Bin Liu,Yulong Bian,Shuang Liang,Meng Yuan,Shuming Dong,Fei He,Shili Gai,Piaoping Yang,Ziyong Cheng,Jun Lin

Recently, various metal peroxide nanomaterials have drawn increasing attention as an efficient hydrogen peroxide (H2O2) self-supplying agent for enhanced tumor therapy. However, a single kind of metal peroxide is insufficient to achieve more effective antitumor performance. Here, a hyaluronic acid modified calcium and copper peroxides nanocomposite has been synthesized by a simple one-step strategy. After effective accumulation at the tumor site due to the enhanced permeability and retention (EPR) effect and specific recognition of hyaluronate acid with CD44 protein on the surface of tumor cells, plenty of Ca2+, Cu2+, and H2O2 can be simultaneously released in acid and hyaluronidase overexpressed tumor microenvironment (TME), generating abundant hydroxyl radical through enhanced Fenton-type reaction between Cu2+ and self-supplying H2O2 with the assistance of glutathione depletion. Overloaded Ca2+ can lead to mitochondria injury and thus enhance the oxidative stress in tumor cells. Moreover, an unbalanced calcium transport channel caused by oxidative stress can further promote tumor calcification and necrosis, which is generally defined as ion-interference therapy. As a result, the synergistic effect of Fenton-like reaction by Cu2+ and mitochondria dysfunction by Ca2+ in ROS generation is performed. Therefore, a TME-responsive calcium and copper peroxides nanocomposite based on one-step integration has been successfully established and exhibits a more satisfactory antitumor efficiency than any single kind of metal peroxide.

研究领域: 癌症治疗 · 纳米技术 · 材料科学 · 生物化学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Investigation on chain segment motions of various starch molecules under different glycerol-water system

Liping Mei,Zhijie Zhu,Caihong Wang,Chengyi Sun,Peirong Chen,Huimei Cai,Xu Chen,Xianfeng Du

The molecular motion of starch at different glycerol concentrations (0, 20, 50, and 80 %) was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. Fourier-transform infrared (FTIR) spectroscopy and 1 H nuclear magnetic resonance ( 1 H NMR) spectroscopy confirmed that hydroxyl groups at the C2 and C3 positions of glucose units in corn starch (CS), waxy corn starch (WCS), and high amylose corn starch (HCS) were labeled with 4-amino-TEMPO. The crystallinities of CS, WCS, and HCS after spin-labeling decreased from 30.68 % to 3.21 %, 39.36 % to 1.65 %, and 28.54 % to 8.08 %, respectively. The pseudoplastic fluid properties of the spin-labeled starch remained shear-thin at different glycerol concentrations. EPR revealed the fast- and slow-motion components of the spin-labeled starch molecules dispersed in water. At a glycerol concentration of 20 %, the slow-motion component disappeared, indicating a faster rotational motion of the starch chain segments. As the glycerol concentration increased to 50 and 80 %, the rotational motion slowed because of high viscosity. In particular, the mobility of the spin-labeled WCS chains increased owing to easier access of glycerol and water to the branched structure. This study directly observed the dynamics of the molecular behavior of starch in glycerol-water systems.

CAS / MDL: 64-17-5 67-68-5 822-06-0
研究领域: 食品科学 · 物理化学 · 材料科学
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Nano Today · 2022 · IF 18.962

Transdermal delivery system based on heparin-modified graphene oxide for deep transportation, tumor microenvironment regulation, and immune activation

Xiyou Du,Xiaoye Yang,Yu Zhang,Shan Gao,Shangui Liu,Jianbo Ji,Guangxi Zhai

Enhancing skin penetration and facilitating tumor infiltration in melanoma treatment through transdermal administration remains an intractable challenge. In the present study, docetaxel- and 1-methyl- D -tryptophan-loaded heparin-modified graphene oxide (D-1/GH) nanosheets were developed to overcome these barriers. Through heparin (Hep)-mediated stratum corneum (SC) hydration, D-1/GH permeates the skin through the intercellular route and the appendage pathway. Based on the relatively leaky structure of the tumor and the high affinity of Hep for tumors, D-1/GH can infiltrate tumors. Subsequently, D-1/GH is transported to deeper tumors through blood and lymphatic vessels. Theoretically, D-1/GH is wrapped in lymphatic vessels through the lymphatic vessel endothelial receptor-1 (LYVE-1)-mediated lymphatic transmigratory cup structure and enters blood vessels through the enhanced permeation and retention (EPR) effect, which is reported here for the first time. D-1/GH-mediated combinational therapy augments the therapeutic effect of chemotherapy and photothermal therapy (PTT) while inducing immunogenic cell death (ICD), thereby recruiting immune cells , and eliciting an immune response. D-1/GH reverses the immunosuppressive tumor microenvironment to potentiate the immune response, thus suppressing abscopal tumors and lung metastases. Collectively, this study identified a novel permeation mode, providing a new perspective to improve antitumor efficacy, boost immune response, and avert systemic distribution.

研究领域: 药学 · 纳米技术 · 肿瘤学 · 免疫学
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DRUG DELIVERY · 2020 · IF 4.902

Furin-responsive triterpenine-based liposomal complex enhances anticervical cancer therapy through size modulation

Yunyan Chen,Mengfei Guo,Ding Qu,Yuping Liu,Jian Guo,Yan Chen

The accumulation and penetration of antitumor drugs in tumor tissues are directly related to their antitumor effects. The particle size of the nanodrug delivery system is one of the most important factors for the accumulation and penetration of antitumor drugs within tumor tissues. Generally, nanodelivery systems of intermediate size (100–120 nm) are capable of efficient accumulation owing to prolonged circulation and enhanced permeability and retention (EPR) effect; however, smaller ones (20–40 nm) are effective for deep penetration within tumor tissue. Currently a conventional drug delivery system cannot possess two types of optimal sizes, simultaneously. To solve this and to enhance cervical cancer treatment, a furin-responsive triterpenine-based liposomal complex (PEGcleavable Tf-CTM/L), with Tf-CTM (transferrin-modified tripterine-loaded coix seed oil microemulsion) in core, coated with a thermo-sensitive lipid and a kind of PEG shell modified with a furin-cleavable peptide was developed to improve tumor-specific accumulation and penetration. Herein, PEGcleavable Tf-CTM/L was capable of efficient accumulation because of EPR effect. The PEG shells could timely detach under stimulation of overexpressed furin protein to solve the problem of the steric hindrance dilemma. The small-sized Tf-CTM released under stimulation of tumor microthermal environment in cervical cancer, which was efficient with regards to deep penetration at tumor sites. Notably, compared to the use of triterpenine alone, PEGcleavable Tf-CTM/L promoted anticervical efficacy and displayed diminished systemic toxicity by efficient accumulation and deep penetration of antitumor drugs within tumor tissues. Our study provides a new strategy, and holds promising potential for anticervical cancer treatment.

研究领域: 药学 · 纳米技术 · 癌症研究 · 药物递送系统 · 生物医学工程
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Journal of Environmental Sciences · 2022 · IF 6.796

Boron promoted Fe3+/peracetic acid process for sulfamethazine degradation: Efficiency, role of boron, and identification of the reactive species

Yanhong Zhang,Guangbing Liu,Yuzhu Xue,Lichun Fu,Yawei Qian,Minhui Hou,Xiang Li,Chen Ling,Ying Zhang,Yuwei Pan

In this work, boron (B) was used to promote Fe 3+ /peracetic acid (Fe 3+ /PAA) for the degradation of sulfamethazine (SMT). An SMT degradation efficiency of 9.1% was observed in the Fe 3+ /PAA system over 60 min, which was significantly increased to 99.3% in the B/Fe 3+ /PAA system over 10 min. The B/Fe 3+ /PAA process also exhibited superior resistance to natural substances, excellent adaptability to different harmful substances, and good removal of antibiotics in natural fresh water samples. The mechanism of action of boron for Fe 3+ reduction was determined using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) spectroscopy, density functional theory (DFT) calculations, and electrochemical tests. The dominant role of • OH was confirmed using quenching experiments, electron spin resonance (EPR) spectroscopy, and quantitative tests. Organic radicals (R-O • ) and Fe(IV) also significantly contribute to the removal of SMT. DFT calculations on the reaction between Fe 2+ and the PAA were conducted to further determine the contribution from • OH, R-O • , and Fe(IV) from the perspective of thermodynamics and the reaction pathways. Different boron dosages, Fe 3+ dosages, and initial pH values were also investigated in the B/Fe 3+ /PAA system to study their effect of SMT removal and the production of the reactive species. Fe(IV) production determined the k R-O•+Fe(IV) value suggesting that Fe(IV) may play a more important role than R-O • . A comparison of the results with other processes has also proved that the procedure described in this study (B/Fe 3+ /PAA) is an effective method for the degradation of antibiotics.

研究领域: 环境科学 · 化学工程 · 分析化学 · 材料科学
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INORGANIC CHEMISTRY COMMUNICATIONS · 2023 · IF 3.8

Photothermally driven degradable nanomissile for single-wavelength phototherapy and hypoxia-activated chemotherapy

Feng Ouyang,Li Zhao,Qi Shuai

Viscous tumour tissue seriously affects the effective delivery of nanodrugs and reduces their anti-tumour effect. In order to solve this problem, a nanomotor (Cy7@ZIF-8@TPZ) for penetrating tumour tissue was synthesized. A new amphiphilic molecule Cy7 was designed and synthesized to wrap ZIF-8 loaded with TPZ to obtain the final nanomotor. The synthesized Cy7 can not only realize photodynamic therapy (PDT) and photothermal therapy (PTT) simultaneously under single-wavelength illumination, but also promote the movement of nanoparticles through thermal drive. Through the targeting ability of Cy7 and the enhanced permeability and retention (EPR) effect, the nanomotor can conduct directional deep puncture under illumination. The oxygen continuously consumed by PDT further activates hypoxia-activated chemotherapy, and the combined PTT/PDT/hypoxia-activated CT therapy greatly enhances the anti-tumour efficacy of Cy7@ZIF-8@TPZ. In addition, light-degradable Cy7, acid-degraded ZIF-8 and hypoxia-activated TPZ greatly reduce the side effects of nanomotors.

CAS / MDL: 95-50-1
研究领域: 癌症治疗 · 纳米技术 · 生物医学工程 · 药学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2025 · IF 9.7

Optimizing the electron spin state of hierarchical NiCo2O4@MXene@LDH 3D composite electrode by heterointerface engineering to enhance energy density and excellent cyclic stability of supercapacitor

Jianghong You,Yiming Yuan,Chen Zhang,Haoming Xu,Mingyao Chen,Ying Wang,Dongsheng Chen

The transition metal oxide of nickel cobaltite (NiCo 2 O 4 ) has gained more and more attention from battery industry for its excellent properties of high capacitance and cycling stability. However, its performance when used in supercapacitors is compromised due to its limited active sites and poor conductivity. Herein, a 3D (three-dimensional) hierarchical and high-performance material of NiCo 2 O 4 @MXene@LDH (LDH: layered double hydroxide) composite was designed and synthesized. In the material, NiCo 2 O 4 nanorods form a skeleton of nanosheet arrays on layered MXene; and on the nanosheet arrays, NiCo-LDH nanoparticles are attached to form a 3D hierarchical structure, extending the electrochemically active sites, suppressing the agglomeration of NiCo-LDH and producing hierarchical channels that promote electron and ion transport. Density functional theory (DFT) calculations and the results of Ultraviolet–visible (UV–Vis) spectrophotometry indicated that the introduction of MXene and NiCo-LDH induces a redistribution of the electronic states of NiCo 2 O 4 due to the formation of a heterointerface, thereby decreasing its bandgap by about 1.42 eV. The X-ray photoelectron spectroscopy (XPS) analysis further demonstrated the negative shift in the initial binding energies of nickel (Ni) and cobalt (Co) atoms, which is due to their transition of spin states; and this is in agreement with the high intensity of electron paramagnetic resonance (EPR) peak in the NiCo 2 O 4 @MXene@LDH composite. The in situ Raman analysis reveals that the enhanced energy storage performance originates from the accelerated formation and increased exposure of NiCoOOH active species during electrochemical cycling. The synergistic effect of MXene and NiCo-LDH introduced into NiCo 2 O 4 enhanced the supercapacitor in terms of power and energy densities. It was indicated that the supercapacitor fabricated from NiCo 2 O 4 @MXene@LDH supercapacitor exhibited a specific capacitance of 5066 F g −1 at 1 A g −1 , and a capacitance retention of 97.82 % after 10,000 charge cycles at 10 A g −1 . Moreover, an asymmetric supercapacitor (ASC) device with a NiCo 2 O 4 @MXene@LDH//AC configuration was developed. The supercapacitor presented an energy density and power density of 70.11 Wh kg −1 and 850.22 W kg −1 , respectively. The redistribution of electronic states and decreased bandgap could facilitate the creation of NiCo 2 O 4 -based materials with customized features for supercapacitors.

研究领域: 材料科学 · 电化学 · 纳米技术 · 储能技术 · 表面工程 · 固体物理
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