Biodegradable Nanoprodrugs: “Delivering” ROS to Cancer Cells for Molecular Dynamic Therapy

Biodegradable nanoprodrugs, inheriting the antitumor effects of chemotherapy drugs and overcoming the inevitable drawback of side effects on normal tissues, hold promise as next-generation cancer therapy candidates. Biodegradable nanoprodrugs of transferrin-modified MgO₂ nanosheets are developed to selectively deliver reactive oxygen species to cancer cells for molecular dynamic therapy strategy. The nanosheets favor the acidic and low catalase activity tumor microenvironment to react with proton and release nontoxic Mg²⁺. This reaction simultaneously produces abundant H₂O₂ to induce cell death and damage the structure of transferrin to release Fe³⁺, which will react with H₂O₂ to produce highly toxic ·OH to kill tumor cells.     

Nanocatalysts‐Augmented and Photothermal‐Enhanced Tumor‐Specific Sequential Nanocatalytic Therapy in Both NIR‐I and NIR‐II Biowindows

The tumor microenvironment (TME) has been increasingly recognized as a crucial contributor to tumorigenesis. Based on the unique TME for achieving tumor‐specific therapy, here a novel concept of photothermal‐enhanced sequential nanocatalytic therapy in both NIR‐I and NIR‐II biowindows is proposed, which innovatively changes the condition of nanocatalytic Fenton reaction for production of highly efficient hydroxyl radicals (?OH) and consequently suppressing the tumor growth. Evidence suggests that glucose plays a vital role in powering cancer progression. Encouraged by the oxidation of glucose to gluconic acid and H₂O₂ by glucose oxidase (GOD), an Fe₃O₄/GOD‐functionalized polypyrrole (PPy)‐based composite nanocatalyst is constructed to achieve diagnostic imaging‐guided, photothermal‐enhanced, and TME‐specific sequential nanocatalytic tumor therapy. The consumption of intratumoral glucose by GOD leads to the in situ elevation of the H₂O₂ level, and the integrated Fe₃O₄ component then catalyzes H₂O₂ into highly toxic ?OH to efficiently induce cancer‐cell death. Importantly, the high photothermal‐conversion efficiency (66.4% in NIR‐II biowindow) of the PPy component elevates the local tumor temperature in both NIR‐I and NIR‐II biowindows to substaintially accelerate and improve the nanocatalytic disproportionation degree of H₂O₂ for enhancing the nanocatalytic‐therapeutic efficacy, which successfully achieves a remarkable synergistic anticancer outcome with minimal side effects.     

Fe(III)-Naphthazarin Metal–Phenolic Networks for Glutathione-Depleting Enhanced Ferroptosis–Apoptosis Combined Cancer Therapy

Nowadays, Fenton chemistry-based chemodynamic therapy (CDT) is an emerging approach to killing tumor cells by converting endogenous H₂O₂ into cytotoxic hydroxyl radicals (·OH). However, the elimination of ·OH by intracellular overexpressed glutathione (GSH) results in unsatisfactory antitumor efficiency. In addition, the single mode of consuming GSH and undesirable drug loading efficiency cannot guarantee the efficient cancer cells killing effect. Herein, a simple one-step strategy for the construction of Fe³⁺-naphthazarin metal–phenolic networks (FNP MPNs) with ultrahigh loading capacity, followed by the modification of NH₂-PEG-NH₂, is developed. The carrier-free FNP MPNs can be triggered by acid and GSH, and rapidly release naphthazarin and Fe³⁺, which is further reduced to Fe²⁺ that exerts Fenton catalytic activity to produce abundant ·OH. Meanwhile, the Michael addition between naphthazarin and GSH can lead to GSH depletion and thus achieve tumor microenvironment (TME)-triggered enhanced CDT, followed by activating ferroptosis and apoptosis. In addition, the reduced Fe²⁺ as a T₁-weighted contrast agent endows the FNP MPNs with magnetic resonance imaging (MRI) functionality. Overall, this work is the debut of naphthazarin as ligands to fabricate functional MPNs for effectively depleting GSH, disrupting intracellular redox homeostasis, and enhancing CDT effects, which opens new perspectives on multifunctional MPNs for tumor synergistic therapy.     

A Multifunctional Cascade Bioreactor Based on Hollow‐Structured Cu2MoS4 for Synergetic Cancer Chemo‐Dynamic Therapy/Starvation Therapy/Phototherapy/Immunotherapy with Remarkably Enhanced Efficacy

The unique tumor microenvironment (TME) facilitates cancer proliferation and metastasis, and it is hard to cure cancer completely via monotherapy. Herein, a multifunctional cascade bioreactor based on hollow mesoporous Cu₂MoS₄ (CMS) loaded with glucose oxidase (GOx) is constructed for synergetic cancer therapy by chemo‐dynamic therapy (CDT)/starvation therapy/phototherapy/immunotherapy. The CMS harboring multivalent elements (Cu^1+/2+, Mo^4+/6+) exhibit Fenton‐like, glutathione (GSH) peroxidase‐like and catalase‐like activity. Once internalized into the tumor, CMS could generate ·OH for CDT via Fenton‐like reaction and deplete overexpressed GSH in TME to alleviate antioxidant capability of the tumors. Moreover, under hypoxia TME, the catalase‐like CMS could react with endogenous H₂O₂ to generate O₂ for activating the catalyzed oxidation of glucose by GOx for starvation therapy accompanied with the regeneration of H₂O₂. The regenerated H₂O₂ can devote to Fenton‐like reaction for realizing GOx‐catalysis‐enhanced CDT. Meanwhile, the CMS under 1064 nm laser irradiation shows remarkable tumor‐killing ability by phototherapy due to its excellent photothermal conversion efficiency (η = 63.3%) and cytotoxic superoxide anion (·O₂^?) generation performance. More importantly, the PEGylated CMS@GOx‐based synergistic therapy combined with checkpoint blockade therapy could elicit robust immune responses for both effectively ablating primary tumors and inhibiting cancer metastasis.     

Enhanced Chemodynamic Therapy Mediated by a Tumor-Specific Catalyst in Synergy with Mitophagy Inhibition Improves the Efficacy for Endometrial Cancer

Chemodynamic therapy (CDT) relies on the tumor microenvironment (e.g., high H₂O₂ level) responsive Fenton-like reactions to produce hydroxyl radicals (·OH) against tumors. However, endogenous H₂O₂ is insufficient for effective chemodynamic responses. An NAD(P)H: quinone oxidoreductase 1 (NQO1)^high catalase (CAT)^low therapeutic window for the use of NQO1 bioactive drug β-lapachone (β-Lap) is first identified in endometrial cancer (EC). Accompanied by NADH depletion, NQO1 catalyzes β-Lap to produce excess H₂O₂ and initiate oxidative stress, which selectively suppress NQO1^high EC cell proliferation, induce DNA double-strand breaks, and promote apoptosis. Moreover, shRNA-mediated NQO1 knockdown or dicoumarol rescues NQO1^high EC cells from β-Lap-induced cytotoxicity. Arginine-glycine-aspartic acid (RGD)-functionalized iron-based metal-organic frameworks (MOF(Fe)) further promote the conversion of the accumulated H₂O₂ into highly oxidative ·OH, which in turn, exacerbates the oxidative damage to RGD-positive target cells. Furthermore, mitophagy inhibition by Mdivi-1 blocks a powerful antioxidant defense approach, ultimately ensuring the anti-tumor efficacy of stepwise-amplified reactive oxygen species signals. The tumor growth inhibition rate (TGI) is about 85.92%. However, the TGI of MOF(Fe)-based synergistic antitumor therapy decreases to only 50.46% in NQO1-deficient KLE tumors. Tumor-specific chemotherapy and CDT-triggered therapeutic modality present unprecedented therapeutic benefits in treating NQO1^high EC.     

A Glucose/Oxygen‐Exhausting Nanoreactor for Starvation‐ and Hypoxia‐Activated Sustainable and Cascade Chemo‐Chemodynamic Therapy

Fenton reaction‐mediated chemodynamic therapy (CDT) can kill cancer cells via the conversion of H₂O₂ to highly toxic HO?. However, problems such as insufficient H₂O₂ levels in the tumor tissue and low Fenton reaction efficiency severely limit the performance of CDT. Here, the prodrug tirapazamine (TPZ)‐loaded human serum albumin (HSA)–glucose oxidase (GOx) mixture is prepared and modified with a metal–polyphenol network composed of ferric ions (Fe³⁺) and tannic acid (TA), to obtain a self‐amplified nanoreactor termed HSA–GOx–TPZ–Fe³⁺–TA (HGTFT) for sustainable and cascade cancer therapy with exogenous H₂O₂ production and TA‐accelerated Fe³⁺/Fe²⁺ conversion. The HGTFT nanoreactor can efficiently convert oxygen into HO? for CDT, consume glucose for starvation therapy, and provide a hypoxic environment for TPZ radical‐mediated chemotherapy. Besides, it is revealed that the nanoreactor can significantly elevate the intracellular reactive oxygen species content and hypoxia level, decrease the intracellular glutathione content, and release metal ions in the tumors for metal ion interference therapy (also termed “ion‐interference therapy” or “metal ion therapy”). Further, the nanoreactor can also increase the tumor’s hypoxia level and efficiently inhibit tumor growth. It is believed that this tumor microenvironment‐regulable nanoreactor with sustainable and cascade anticancer performance and excellent biosafety represents an advance in nanomedicine.     

Engineered Bacterial Bioreactor for Tumor Therapy via Fenton‐Like Reaction with Localized H2O2 Generation

Synthetic biology based on bacteria has been displayed in antitumor therapy and shown good performance. In this study, an engineered bacterium Escherichia coli MG1655 is designed with NDH‐2 enzyme (respiratory chain enzyme II) overexpression (Ec‐pE), which can colonize in tumor regions and increase localized H₂O₂ generation. Following from this, magnetic Fe₃O₄ nanoparticles are covalently linked to bacteria to act as a catalyst for a Fenton‐like reaction, which converts H₂O₂ to toxic hydroxyl radicals (?OH) for tumor therapy. In this constructed bioreactor, the Fenton‐like reaction occurs with sustainably synthesized H₂O₂ produced by engineered bacteria, and severe tumor apoptosis is induced via the produced toxic ?OH. These results show that this bioreactor can achieve effective tumor colonization, and realize a self‐supplied therapeutic Fenton‐like reaction without additional H₂O₂ provision.     

NIR Responsive Doxorubicin-Loaded Hollow Copper Ferrite @ Polydopamine for Synergistic Chemodynamic/Photothermal/Chemo-Therapy

Osteosarcoma (OS) is the most serious bone malignancy, and the survival rate has not significantly improved in the past 40 years. Thus, it is urgent to develop a new strategy for OS treatment. Chemodynamic therapy (CDT) as a novel therapeutic method can destroy cancer cells by converting endogenous hydrogen peroxide (H₂O₂) into highly toxic hydroxyl radicals (·OH). However, the therapeutic efficacy of CDT is severely limited by the low catalytic efficiency and overexpressed glutathione (GSH). Herein, an excellent nanocatalytic platform is constructed via a simple solvothermal method using F127 as a soft template to form the hollow copper ferrite (HCF) nanoparticle, followed by the coating of polydopamine on the surface and the loading of doxorubicin (DOX). The Fe³⁺ and Cu²⁺ released from HCF@polydopamine (HCFP) can deplete GSH through the redox reactions, and then trigger the H₂O₂ to generate ·OH by Fenton/Fenton-like reaction, resulting in enhanced CDT efficacy. Impressively, the photothermal effect of HCFP can further enhance the efficiency of CDT and accelerate the release of DOX. Both in vitro and in vivo experiments reveal that the synergistic chemodynamic/photothermal/chemo-therapy exhibits a significantly enhanced anti-OS effect. This work provides a promising strategy for OS treatment.     

Low-temperature fabrication and electrical property of 10 mol% Sm2O3-doped CeO2 ceramics

Ten mol% Sm₂O₃-doped CeO₂ solid-solution (20SDC) powders have been synthesized via carbonate coprecipitation using ammonium hydrogen carbonate (AHC) and urea as the precipitants, respectively. Characterizations were achieved by elemental analysis, X-ray diffractometry, differential thermal analysis/thermogravimetry, and FESEM. An amorphous hydroxyl carbonate precursor (Ce,Sm)(OH)CO₃·2H₂O having nanosized (~10 nm) spherical particles was formed with AHC, while a mixture of crystalline (Ce,Sm)₂(CO₃)₂(OH)₂·H₂O and (Ce,Sm)₂O(CO₃)₂·H₂O phases exhibiting irregular particle morphologies was obtained with urea. Both the precursors convert to oxide solid solutions without any phase detected corresponding to Sm₂O₃ during calcination. The oxide powder processed via the AHC method can be sintered to >99% of the theoretical at a low temperature of 1200 ?C, due to the good dispersion and ultrafine size (~15 nm) of the particles, while that from the urea method can only reach ,67.2% dense at the same temperature. Electrical conductivity of the densified ceramic was measured in air in the range 400—700 ?C by the DC three-point method, and an activation energy of ~60.5 kJ/mol was derived from the experimental data.

© 2003 Elsevier Ltd. All rights reserved.     

Immunomodulation-Enhanced Nanozyme-Based Tumor Catalytic Therapy

Nanozyme-based tumor catalytic therapy has attracted widespread attention in recent years. However, its therapeutic outcomes are diminished by many factors in the tumor microenvironment (TME), such as insufficient endogenous hydrogen peroxide (H₂O₂) concentration, hypoxia, and immunosuppressive microenvironment. Herein, an immunomodulation-enhanced nanozyme-based tumor catalytic therapy strategy is first proposed to achieve the synergism between nanozymes and TME regulation. TGF-β inhibitor (TI)-loaded PEGylated iron manganese silicate nanoparticles (IMSN) (named as IMSN-PEG-TI) are constructed to trigger the therapeutic modality. The results show that IMSN nanozyme exhibits both intrinsic peroxidase-like and catalase-like activities under acidic TME, which can decompose H₂O₂ into hydroxyl radicals (•OH) and oxygen (O₂), respectively. Besides, it is demonstrated that both IMSN and TI can regulate the tumor immune microenvironment, resulting in macrophage polarization from M2 to M1, and thus inducing the regeneration of H₂O₂, which can promote catalytic activities of IMSN nanozyme. The potent antitumor effect of IMSN-PEG-TI is proved by in vitro multicellular tumor spheroids (MCTS) and in vivo CT26-tumor-bearing mice models. It is believed that the immunomodulation-enhanced nanozyme-based tumor treatment strategy is a promising tool to kill cancer cells.     

Mechanism of cerium(III) oxidation with ozone in sulfuric acid solutions

The kinetics of Ce(III) oxidation with ozone in 0.1–3.2 M H₂SO₄ solutions was studied by spectrophotometry. The reaction follows the first-order rate law with respect to each reactant. The rate constant k slightly increases with an increase in the acid concentration, which is associated with an increase in the O₃/O ₃ ^? oxidation potential. The activation energy in the range 17–35°C is 46 kJ mol^?1. With excess Ce(III), the stoichiometric coefficient Δ[Ce(IV)]/Δ[O₃] increases from 1.6 to 2 in going from 0.1 to 1–3.2 M H₂SO₄. The extent of the Ce(III) oxidation is 78% in 0.1 M H₂SO₄ and reaches 82% in 1 M H₂SO₄. The ozonation involves the reactions Ce(III) + O₃ → Ce(IV) + O ₃ ^? , O ₃ ^? + H⁺ → HO₃, HO₃ → OH + O₂, OH + HSO ₄ ^? → H₂O + SO ₄ ^? , OH + Ce(III) → OH^? + Ce(IV), and SO ₄ ^? + Ce(III) → SO_4/2? + Ce(IV). Low stoichiometric coefficient of the Ce(III) oxidation is associated with the hydrolysis of Ce(IV). The excited Ce(IV) ion arising from oxidation of Ce(III) with OH radical forms with the hydrolyzed Ce(IV) ion a dimer whose decomposition yields Ce(III) and H₂O₂. After the ozonation termination, Ce(IV) is relatively stable in sulfuric acid solution, with only 5–7% of Ce(IV) disappearing in 24 h.     

A Mesoporous Nanoenzyme Derived from Metal–Organic Frameworks with Endogenous Oxygen Generation to Alleviate Tumor Hypoxia for Significantly Enhanced Photodynamic Therapy

Tumor hypoxia compromises the therapeutic efficiency of photodynamic therapy (PDT) as the local oxygen concentration plays an important role in the generation of cytotoxic singlet oxygen (¹O₂). Herein, a versatile mesoporous nanoenzyme (NE) derived from metal–organic frameworks (MOFs) is presented for in situ generation of endogenous O₂ to enhance the PDT efficacy under bioimaging guidance. The mesoporous NE is constructed by first coating a manganese‐based MOFs with mesoporous silica, followed by a facile annealing process under the ambient atmosphere. After removing the mesoporous silica shell and post‐modifying with polydopamine and poly(ethylene glycol) for improving the biocompatibility, the obtained mesoporous NE is loaded with chlorin e6 (Ce6), a commonly used photosensitizer in PDT, with a high loading capacity. Upon the O₂ generation through the catalytic reaction between the catalytic amount NE and the endogenous H₂O₂, the hypoxic tumor microenvironment is relieved. Thus, Ce6‐loaded NE serves as a H₂O₂‐activated oxygen supplier to increase the local O₂ concentration for significantly enhanced antitumor PDT efficacy in vitro and in vivo. In addition, the NE also shows T₂‐weighted magnetic resonance imaging ability for its in vivo tracking. This work presents an interesting biomedical use of MOF‐derived mesoporous NE as a multifunctional theranostic agent in cancer therapy.     

A Cascade Nanoreactor of Metal-Protein-Polyphenol Capsule for Oxygen-Mediated Synergistic Tumor Starvation and Chemodynamic Therapy

Starvation therapy kills tumor cells via consuming glucose to cut off their energy supply. However, since glucose oxidase (GOx)-mediated glycolysis is oxygen-dependent, the cascade reaction based on GOx faces the challenge of a hypoxic tumor microenvironment. By decomposition of glycolysis production of H₂O₂ into O₂, starvation therapy can be enhanced, but chemodynamic therapy is limited. Here, a close-loop strategy for on demand H₂O₂ and O₂ delivery, release, and recycling is proposed. The nanoreactor (metal-protein-polyphenol capsule) is designed by incorporating two native proteins, GOx and hemoglobin (Hb), in polyphenol networks with zeolitic imidazolate framework as sacrificial templates. Glycolysis occurs in the presence of GOx with O₂ consumption and the produced H₂O₂ reacts with Hb to produce highly cytotoxic hydroxyl radicals (•OH) and methemoglobin (MHb) (Fenton reaction). Benefiting from the different oxygen carrying capacities of Hb and MHb, oxygen on Hb is rapidly released to supplement its consumption during glycolysis. Glycolysis and Fenton reactions are mutually reinforced by oxygen supply, consuming more glucose and producing more hydroxyl radicals and ultimately enhancing both starvation therapy and chemodynamic therapy. This cascade nanoreactor exhibits high efficiency for tumor suppression and provides an effective strategy for oxygen-mediated synergistic starvation therapy and chemodynamic therapy.     

Synthesis of hexagonal Zn3(OH)2V2O7·2H2O nanoplates by a hydrothermal approach: Magnetic and photocatalytic properties

Hexagonal Zn₃(OH)₂V₂O₇·2H₂O nanoplates have been successfully synthesized via a facile and template-free hydrothermal method. The nanocrystals have a hexagonal shape with 650–750 nm in diameter and 120–140 nm in thickness. The possible mechanism of forming such hexagonal Zn₃(OH)₂V₂O₇·2H₂O nanoplates may be due to its inherent anisotropic crystal structure. Magnetic hysteresis measurement indicates that the as-synthesized hexagonal Zn₃(OH)₂V₂O₇·2H₂O nanoplates have weak ferromagnetic property at room temperature. Compared to the floriated-like nanostructured Zn₃V₂O₇(OH)₂(H₂O)₂ synthesized by a hydrothermal route, the as-prepared hexagonal Zn₃(OH)₂V₂O₇·2H₂O nanoplates exhibited a significant increase in the methylene blue (MB) photodegradation rate under UV irradiation.     

A novel biomimetic catalyst constructed by axial coordination of hemin with PAN fiber for efficient degradation of organic dyes

A novel biomimetic catalyst was synthesized by supporting hemin onto the amidoximated polyacrylonitrile (PAN) fiber and then used for the oxidative degradation of organic dyes by H₂O₂ activation. SEM, FTIR and XPS results suggested that the OH and NH₂ in amidoxime groups were responsible for hemin immobilization through axial coordination bonds. The fibrous support significantly enhanced the catalytic activity and pH tolerance of pure hemin, and the prepared catalyst also exhibited excellent recycling capability. In addition, the effect of axial ligands on the catalytic mechanism was clarified by employing the modified PAN fiber with amidrazones groups as the support of hemin, and the possible catalytic mechanism was proposed and discussed based on the ESR measurement combined with a series of designed experiments. It is found that OH and NH₂ as axial ligands of hemin might induce H₂O₂ activation through two different pathways, corresponding to the generation of Fe(IV)=O and ^·OH species, respectively.     

Carrier-Free H2O2 Self-Supplier for Amplified Synergistic Tumor Therapy

Chemodynamic therapy (CDT) utilizes Fenton or Fenton-like reactions to convert hydrogen peroxide (H₂O₂) into cytotoxic hydroxyl radicals (•OH) and draws extensive interest in tumor therapy. Nevertheless, high concentrations of glutathione (GSH) and insufficient endogenous H₂O₂ often cause unsatisfactory therapeutic efficacy. Herein, a GSH-depleting and H₂O₂ self-providing carrier-free nanomedicine that can efficiently load indocyanine green (ICG), β-lapachone (LAP), and copper ion (Cu²⁺) (ICG-Cu²⁺-LAP, LICN) to mediate synergetic photothermal and chemotherapy in enhanced chemodynamic therapy is designed. The results show that  LICNs successfully enter tumors owing to the enhanced permeability and retention effect. Through the reductive intracellular environment, Cu²⁺ in LICN can react with intracellular GSH, alleviate the antioxidant capacity of tumor tissues, and trigger the release of drugs. When LICN is subjected to near-infrared (NIR) irradiation, enhanced photothermal effect and upregulated expression of NAD(P)H quinone oxidoreductase-1 (NQO1) are observed. Meanwhile, the released LAP not only supports chemotherapy but also catalyzes NQO1 and produces sufficient endogenous H₂O₂, thereby increasing the efficiency of Cu⁺-based Fenton-like reaction. Notably, GSH depletion and H₂O₂ self-sufficiency generate sufficient •OH and kill tumor cells with high specificity. Overall, the study provides an innovative strategy to self-regulate GSH and H₂O₂ levels for effective anticancer therapy.     

Programmable NIR‐II Photothermal‐Enhanced Starvation‐Primed Chemodynamic Therapy using Glucose Oxidase‐Functionalized Ancient Pigment Nanosheets

Chemodynamic therapy (CDT) has attracted considerable attention recently, but the poor reaction kinetics restrict its practical utility in clinic. Herein, glucose oxidase (GOx) functionalized ancient pigment nanosheets (SrCuSi₄O₁₀, SC) for programmable near‐infrared II (NIR‐II) photothermal‐enhanced starvation primed CDT is developed. The SC nanosheets (SC NSs) are readily exfoliated from SC bulk suspension in water and subsequently functionalized with GOx to form the nanocatalyst (denoted as SC@G NSs). Upon laser irradiation, the photothermal effect of SC NSs can enhance the catalytic activity of GOx for NIR‐II photothermal‐enhanced starvation therapy, which effectively eliminates intratumoral glucose and produces abundant hydrogen peroxide (H₂O₂). Importantly, the high photothermal‐conversion efficiency (46.3%) of SC@G NSs in second biological window permits photothermal therapy of deep‐seated tumors under the guidance of NIR‐II photoacoustic imaging. Moreover, the acidity amplification due to gluconic acid generation will in turn accelerate the degradation of SC NSs, facilitating the release of strontium (Sr) and copper (Cu) ions. Both the elevated H₂O₂ and the released ions will prime the Cu²⁺/Sr²⁺‐H₂O₂ reaction for enhanced CDT. Thus, a programmable NIR‐II photothermal‐enhanced starvation primed CDT is established to combat cancer with minimal side effects.     

Surface and structural characterisation of coprecipitated CexZr1?xO2 (0?≤?x?≤?1) mixed oxides

Ce _x Zr_1−x O₂-mixed oxides with three different Ce/Zr ratios (Ce_0.8Zr_0.2O₂, Ce_0.5Zr_0.5O₂ and Ce_0.2Zr_0.8O₂) along with pure cerium and zirconium oxides were prepared by coprecipitation of the metal hydroxides in alkali media and subsequent calcinations at 500 °C, using two different cerium precursors (Ce(NO₃)₃·6H₂O or (NH₄)₂Ce(NO₃)₆). These samples were characterised by N₂ adsorption at −196 °C, XRD, Raman spectroscopy, XPS and H₂-temperature programmed reduction. Besides, the two mixed oxides with higher cerium content were calcined at higher temperature (1000 °C) with the additional purpose of studying their thermal stability and phase homogeneity. XRD and Raman spectroscopy confirm a significant improvement in the insertion of zirconium cations into the ceria lattice when the samples Ce_0.8Zr_0.2O₂ and Ce_0.5Zr_0.5O₂ are synthesised with (NH₄)₂Ce(NO₃)₆ instead of Ce(NO₃)₃·6H₂O. This is attributed to a more homogeneous coprecipitation of cerium and zirconium hydroxides, leading to mixed oxides with better bulk oxygen mobility and smaller lattice parameter. Moreover, the mixed oxides prepared with the (NH₄)₂Ce(NO₃)₆ precursor and calcined at 1000 °C exhibit a single phase whereas phase segregation occurs in the counterpart mixed oxides prepared with the Ce(NO₃)₃·6H₂O precursor. XPS analysis reveal correlations among O/(Ce + Zr) surface atomic ratio and total cerium content for both cerium precursors. Among the samples calcined at 1000 °C, Ce_0.8Zr_0.2O₂ synthesised with Ce(NO₃)₃·6H₂O is the only one that preserves the low-temperature surface reduction peak, and also shows a BET surface area slightly higher than those of the rest of samples calcined at high temperature.     

MOF‐Derived CuS@Cu‐BTC Composites as High‐Performance Anodes for Lithium‐Ion Batteries

The CuS(x wt%)@Cu‐BTC (BTC = 1,3,5‐benzenetricarboxylate; x = 3, 10, 33, 58, 70, 99.9) materials are synthesized by a facile sulfidation reaction. The composites are composed of octahedral Cu₃(BTC)₂·(H₂O)₃ (Cu‐BTC) with a large specific surface area and CuS with a high conductivity. The as‐prepared CuS@Cu‐BTC products are first applied as the anodes of lithium‐ion batteries (LIBs). The synergistic effect between Cu‐BTC and CuS components can not only accommodate the volume change and stress relaxation of electrodes but also facilitate the fast transport of Li ions. Thus, it can greatly suppress the transformation process from Li₂S to polysulfides by improving the reversibility of the conversion reaction. Benefiting from the unique structural features, the optimal CuS(70 wt%)@Cu‐BTC sample exhibits a remarkably improved electrochemical performance, showing an over‐theoretical capacity up to 1609 mAh g^?1 after 200 cycles (100 mA g^?1) with an excellent rate‐capability of ≈490 mAh g^?1 at 1000 mA g^?1. The outstanding LIB properties indicate that the CuS(70 wt%)@Cu‐BTC sample is a highly desirable electrode material candidate for high‐performance LIBs.     

Zn3V2O7(OH)2·2H2O and Zn3(VO4)2 3D microspheres as anode materials for lithium-ion batteries

Three-dimensional Zn₃V₂O₇(OH)₂·2H₂O microspheres have been successfully synthesized by a simple and facile liquid phase precipitation method without using any surfactants or additives. The as-prepared microspheres were constructed by two-dimensional nanosheets, which interconnected with each other through self-assembly. The influences of the aging time, reaction temperature, and pH value on the morphologies of the products were systematically investigated. Moreover, three-dimensional Zn₃(VO₄)₂ microspheres could be formed through calcination of the Zn₃V₂O₇(OH)₂·2H₂O precursor. The obtained Zn₃V₂O₇(OH)₂·2H₂O and Zn₃(VO₄)₂ microspheres were further investigated as the anode materials of lithium-ion batteries. Electrochemical measurements showed that the Zn₃V₂O₇(OH)₂·2H₂O and Zn₃(VO₄)₂ microspheres exhibited high discharge capacity and good cycle stability, indicating potential anode candidates in advanced rechargeable lithium-ion batteries. It should be noted that this is the first report on the Zn₃V₂O₇(OH)₂·2H₂O and Zn₃(VO₄)₂ three-dimensional microspheres as anode materials in lithium-ion batteries. The present work will greatly expand the range of anode choices and could assist long-term endeavors in developing high capacity anode materials for lithium-ion batteries.