A High‐Energy Aqueous Aluminum‐Manganese Battery

Rechargeable aluminum‐ion batteries have drawn considerable attention as a new energy storage system, but their applications are still significantly impeded by critical issues such as low energy density and the lack of excellent electrolytes. Herein, a high‐energy aluminum‐manganese battery is fabricated by using a Birnessite MnO₂ cathode, which can be greatly optimized by a divalence manganese ions (Mn²⁺) electrolyte pre‐addition strategy. The battery exhibits a remarkable energy density of 620 Wh kg^?1 (based on the Birnessite MnO₂ material) and a capacity retention above 320 mAh g^?1 for over 65 cycles, much superior to that with no Mn²⁺ pre‐addition. The electrochemical reactions of the battery are scrutinized by a series of analysis techniques, indicating that the Birnessite MnO₂ pristine cathode is first reduced as Mn²⁺ to dissolve in the electrolyte upon discharge, and Al_xMn_(1?x)O₂ is then generated upon charge, serving as a reversible cathode active material in following cycles. This work provides new opportunities for the development of high‐performance and low‐cost aqueous aluminum‐ion batteries for prospective applications.     

Multifunctional Graphene Oxide‐based Triple Stimuli‐Responsive Nanotheranostics

Construction of multifunctional stimuli‐responsive nanosystems intelligently responsive to inner physiological and/or external irradiations based on nanobiotechnology can enable the on‐demand drug release and improved diagnostic imaging to mitigate the side‐effects of anticancer drugs and enhance the diagnostic/therapeutic outcome simultaneously. Here, a triple‐functional stimuli‐responsive nanosystem based on the co‐integration of superparamagnetic Fe₃O₄ and paramagnetic MnO_x nanoparticles (NPs) onto exfoliated graphene oxide (GO) nanosheets by a novel and efficient double redox strategy (DRS) is reported. Aromatic anticancer drug molecules can interact with GO nanosheets through supramolecular π stacking to achieve high drug loading capacity and pH‐responsive drug releasing performance. The integrated MnO_x NPs can disintegrate in mild acidic and reduction environment to realize the highly efficient pH‐responsive and reduction‐triggered T₁‐weighted magnetic resonance imaging (MRI). Superparamagnetic Fe₃O₄ NPs can not only function as the T₂‐weighted contrast agents for MRI, but also response to the external magnetic field for magnetic hyperthermia against cancer. Importantly, the constructed biocompatible GO‐based nanoplatform can inhibit the metastasis of cancer cells by downregulating the expression of metastasis‐related proteins, and anticancer drug‐loaded carrier can significantly reverse the multidrug resistance (MDR) of cancer cells.     

Mimicking Drug–Substrate Interaction: A Smart Bioinspired Technology for the Fabrication of Theranostic Nanoprobes

Versatile bioinspired strategies are urgently needed to fabricate high‐performance nanoprobes for biomedical application. Herein, a novel bioinspired technology of mimicking drug–substrate interaction is reported for the fabrication of high‐performance nanoprobes. As a proof of concept, a multifunctional bovine serum albumin (BSA)‐MnO₂ nanoparticle‐based nanoplatform is strategically engineered via mimicking the disinfection process of KMnO₄ in an extremely facile way. The prepared BSA‐MnO₂ nanoparticles possess sub‐10 nm and uniform size, excellent colloidal stability, and impressive T ₁ relaxivity of 7.9 mm ^?1 s^?1. The proposed nanoprobe could not only be employed as a high‐performance magnetic resonance imaging (MRI) agent for tumor and renal imaging but can also provide a platform for integrating therapeutic strategies toward tumors. The universal strategy could also be easily extended to the fabrication of other nanoprobes for MR imaging in vivo using other bioactive proteins including ovalbumin and transferrin. This work will open a new way for the development of biomaterials in biomedicine applications.     

One‐Step Solvent‐Free Synthesis and Characterization of Zn1−xMnxSe@C Nanorods and Nanowires

The carbon‐encapsulated, Mn‐doped ZnSe (Zn_1−xMn_xSe@C) nanowires, nanorods, and nanoparticles are synthesized by the solvent‐free, one‐step RAPET (reactions under autogenic pressure at elevated temperature) approach. The aspect ratio of the nanowires/nanorods is altered according to the Mn/Zn atomic ratio, with the maximum being observed for Mn/Zn = 1:20. A 10–20 nm amorphous carbon shell is evidenced from electron microscopy analysis. The replacement of Zn by Mn in the Zn_1−xMn_xSe lattice is confirmed by the hyperfine splitting values in the electron paramagnetic resonance (EPR) experiments. Raman experiments reveal that the Zn_1−xMn_xSe core is highly crystalline, while the shell consists of disordered graphitic carbon. Variable‐temperature cathodoluminescence measurements are performed for all samples and show distinct ZnSe near‐band‐edge and Mn‐related emissions. An intense and broad Mn‐related emission at the largest Mn alloy composition of 19.9% is further consistent with an efficient incorporation of Mn within the host ZnSe lattice. The formation of the core/shell nanowires and nanorods in the absence of any template or structure‐directing agent is controlled kinetically by the Zn_1−xMn_xSe nucleus formation and subsequent carbon encapsulation. Mn replaces Zn mainly in the (111) plane and catalyzes the nanowire growth in the [111] direction.     

Interdispersed Amorphous MnOx–Carbon Nanocomposites with Superior Electrochemical Performance as Lithium‐Storage Material

The realization of manganese oxide anode materials for lithium‐ion batteries is hindered by inferior cycle stability, rate capability, and high overpotential induced by the agglomeration of manganese metal grains, low conductivity of manganese oxide, and the high stress/strain in the crystalline manganese oxide structure during the repeated lithiation/delithiation process. To overcome these challenges, unique amorphous MnO_x–C nanocomposite particles with interdispersed carbon are synthesized using aerosol spray pyrolysis. The carbon filled in the pores of amorphous MnO_x blocks the penetration of liquid electrolyte to the inside of MnO_x, thus reducing the formation of a solid electrolyte interphase and lowering the irreversible capacity. The high electronic and lithium‐ion conductivity of carbon also enhances the rate capability. Moreover, the interdispersed carbon functions as a barrier structure to prevent manganese grain agglomeration. The amorphous structure of MnO_x brings additional benefits by reducing the stress/strain of the conversion reaction, thus lowering lithiation/delithiation overpotential. As the result, the amorphous MnO_x‐C particles demonstrated the best performance as an anode material for lithium‐ion batteries to date.     

A Visible‐ and NIR‐Light Responsive Photothermal Therapy Agent by Chirality‐Dependent MoO3−x Nanoparticles

Chirality‐based semiconducting nanocrystals, as an emerging area, are envisioned to have great potential in chiral sensing, biomedicine, and chiroptical devices. Herein, chiral substoichiometric molybdenum oxide (l /d ‐Cys‐MoO_3?x) nanoparticles are synthesized via step‐by‐step reduction treatment with chiral cysteine molecules. The obtained nanoparticles are used as visible‐ and near‐infrared‐light dual responsive photothermal therapy agent for tumor cell ablation. Notably, the chiral nanoparticles show chiral selectivity for incident light, i.e., when irradiated by left‐circularly polarized light, l ‐Cys‐MoO_3?x is the most sensitive agent giving the highest mortality for HeLa cell ablation in vitro, and vice versa for right‐circularly polarized light with d ‐Cys‐MoO_3?x. In comparison to traditional photothermal therapy with near‐field light source, the investigations with chiral visible light at 532 nm indicate the possibility of chiral Cys‐MoO_3?x nanoparticles for visible light‐based phototherapy via metal–ligand charge transfer chirality, which provides insights for new methods in nanotechnology supported photothermal treatments.     

Spatially Separated CdS Shells Exposed with Reduction Surfaces for Enhancing Photocatalytic Hydrogen Evolution

To the photocatalytic H₂ evolution, the exposure of a reduction surface over a catalyst plays an important role for the reduction of hydrogen protons. Here, this study demonstrates the design of a noble‐metal‐free spatially separated photocatalytic system exposed with reduction surfaces (MnO_x @CdS/CoP) for highly solar‐light‐driven H₂ evolution activity. CoP and MnO_x nanoparticles are employed as the electron and hole collectors, which are selectively anchored on the outer and inner surface of CdS shells, respectively. Under solar light irradiation, the photogenerated holes and electrons can directionally move to the MnO_x and CoP, respectively, leading to the exposure of a reduction surface. As a result, the H₂ evolution increases from 32.0 to 238.4 µmol h^?1, which is even higher than the activity of platinum‐loaded photocatalyst (MnO_x @CdS/Pt). Compared to the pure CdS with serious photocorrosion, the MnO_x @CdS/CoP maintains a changeless activity for the H₂ evolution and rhodamine B degradation, even after four cycles. The research provides a new strategy for the preparation of spatially separated photocatalysts with a selective reduction surface.     

Metal–Organic Framework (MOF) Derived Electrodes with Robust and Fast Lithium Storage for Li‐Ion Hybrid Capacitors

Hybrid metal–organic frameworks (MOFs) demonstrate great promise as ideal electrode materials for energy‐related applications. Herein, a well‐organized interleaved composite of graphene‐like nanosheets embedded with MnO₂ nanoparticles (MnO₂@C‐NS) using a manganese‐based MOF and employed as a promising anode material for Li‐ion hybrid capacitor (LIHC) is engineered. This unique hybrid architecture shows intriguing electrochemical properties including high reversible specific capacity 1054 mAh g^?1 (close to the theoretical capacity of MnO₂, 1232 mAh g^?1) at 0.1 A g^?1 with remarkable rate capability and cyclic stability (90% over 1000 cycles). Such a remarkable performance may be assigned to the hierarchical porous ultrathin carbon nanosheets and tightly attached MnO₂ nanoparticles, which provide structural stability and low contact resistance during repetitive lithiation/delithiation processes. Moreover, a novel LIHC is assembled using a MnO₂@C‐NS anode and MOF derived ultrathin nanoporous carbon nanosheets (derived from other potassium‐based MOFs) cathode materials. The LIHC full‐cell delivers an ultrahigh specific energy of 166 Wh kg^?1 at 550 W kg^?1 and maintained to 49.2 Wh kg^?1 even at high specific power of 3.5 kW kg^?1 as well as long cycling stability (91% over 5000 cycles). This work opens new opportunities for designing advanced MOF derived electrodes for next‐generation energy storage devices.     

Advances in Manganese‐Based Oxides Cathodic Electrocatalysts for Li–Air Batteries

Li–air batteries, characteristic of superhigh theoretical specific energy density, cost‐efficiency, and environment‐friendly merits, have aroused ever‐increasing attention. Nevertheless, relatively low Coulomb efficiency, severe potential hysteresis, and poor rate capability, which mainly result from sluggish oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) kinetics, as well as pitiful cycle stability caused by parasitic reactions, extremely limit their practical applications. Manganese (Mn)‐based oxides and their composites can exhibit high ORR and OER activities, reduce charge/discharge overpotential, and improve the cycling stability when used as cathodic catalyst materials. Herein, energy storage mechanisms for Li–air batteries are summarized, followed by a systematic overview of the progress of manganese‐based oxides (MnO₂ with different crystal structures, MnO, MnOOH, Mn₂O₃, Mn₃O₄, MnOx, perovskite‐type and spinel‐type manganese oxides, etc.) cathodic materials for Li–air batteries in the recent years. The focus lies on the effects of crystal structure, design strategy, chemical composition, and microscopic physical parameters on ORR and OER activities of various Mn‐based oxides, and even the overall performance of Li–air batteries. Finally, a prospect of the research for Mn‐based oxides cathodic catalysts in the future is made, and some new insights for more reasonable design of Mn‐based oxides electrocatalysts with higher catalytic efficiency are provided.     

Proton Conduction in a Tyrosine‐Rich Peptide/Manganese Oxide Hybrid Nanofilm

Proton conduction is an essential process that regulates an integral part of several enzymatic catalyses and bioenergetics. Proton flows in biological entities are sensitively controlled by several mechanisms. To understand and manipulate proton conduction in biosystems, several studies have investigated bulk proton conduction in biomaterials such as polyaspartic acid, collagen, reflectin, serum albumin mats, and eumelanin. However, little is known about the bulk proton conductivity of short peptides and their sequence‐dependent behavior. Here, this paper focuses on a short tyrosine‐rich peptide that has redox‐active and cross‐linkable phenol groups. The spin‐coated peptide nanofilm is immersed in potassium permanganate solution to induce cross‐linking and oxidation, simultaneously leading to hybridization with manganese oxide (MnO_x ). The peptide/MnO_x hybrid nanofilm can efficiently transport protons, and its proton conductivity is ≈18.6 mS cm^?1 at room temperature. This value is much higher than that of biomaterials and comparable to those of other synthetic proton‐conducting materials. These results suggest that peptide‐based hybrid materials can be a promising new class of proton conductor.     

Luminescent Core/Shell Nanoparticles with a Rhabdophane LnPO4‐xH2O Structure: Stabilization of Ce3+‐Doped Compositions

The core/shell strategy has been successfully developed for rhabdophane lanthanide phosphate aqueous colloids. The growth of a LaPO₄‐xH₂O shell around Ce,Tb‐doped core nanoparticles increases their stability against oxidation. A bright green luminescence is thus preserved in sol–gel films whose fabrication requires silica coating and thermal treatment of the core/shell nanoparticles.     

Enhanced Magnetic Anisotropy and Orbital Symmetry Breaking in Manganite Heterostructures

Manipulating magnetic anisotropy in complex oxide heterostructures has attracted much attention. Here, three interface‐engineering approaches are applied to address two general issues with controlling magnetic anisotropy in the La_2/3Sr_1/3MnO₃ heterostructure. One is the paradox arising from the competition between Mn_3d–O_2p orbital hybridization and MnO₆ crystal field. The other is the interfacial region where the nonuniform Mn? O bond length d and Mn? O? Mn bond angle θ disturb the structural modulation. When the interfacial region is suppressed in the interface‐engineered samples, the lateral magnetic anisotropy energy is increased eighteen times. The d‐mediated anisotropic crystal filed that overwhelms the orbital hybridization causes the lateral symmetry breaking of the Mn 3d_x²_?y² orbital, resulting in enhanced magnetic anisotropy. This is different from the classic Jahn–Teller effect where the lateral symmetry is always preserved. Moreover, the quantitative analysis on X‐ray linear dichroism data suggests a direct correlation between Mn 3d_x²_?y² orbital symmetry breaking and magnetic anisotropy energy. The findings not only advance the understanding of magnetic anisotropy in manganite heterostructures but also can be extended to other complex oxides and perovskite materials with correlated degrees of freedom.     

Nanoscale‐Coordination‐Polymer‐Shelled Manganese Dioxide Composite Nanoparticles: A Multistage Redox/pH/H2O2‐Responsive Cancer Theranostic Nanoplatform

Nanoscale coordination polymers (NCPs) self‐assembled from metal ions and organic bridging ligands exhibit many unique features promising for applications in nanomedicine. In this work, manganese dioxide (MnO₂) nanoparticles stabilized by bovine serum albumin are encapsulated by NCP‐shells constructed based on high‐Z element hafnium (Hf) ions and c,c,t‐(diamminedichlorodisuccinato)Pt(IV) (DSP), a cisplatin prodrug. After further modification with polyethylene glycol (PEG), the formed BM@NCP(DSP)‐PEG can simultaneously serve as a radio‐sensitizer owing to the strong X‐ray attenuation capability of Hf to enhance radiotherapy, as well as a chemotherapeutic agent resulting from the reduction‐induced release of cisplatin. Meanwhile, the in situ generated oxygen resulting from MnO₂‐triggered decomposition of tumor endogenous H₂O₂ will be greatly helpful for overcoming hypoxia‐associated radio‐resistance. Upon intravenous injection, BM@NCP(DSP)‐PEG shows efficient tumor homing as well as rapid renal excretion, as illustrated by magnetic resonance imaging and confirmed by biodistribution measurement. Notably, an excellent in vivo tumor growth inhibition effect is observed with BM@NCP(DSP)‐PEG nanoparticles after the combined chemoradiotherapy treatment. Therefore, the NCP‐based composite nanoparticles with inherent biodegradability and no appreciable in vivo toxicity may be a unique type of multifunctional nanoplatform responsive to different parameters in the tumor microenvironment, promising for cancer theranostics with great efficacy.     

Growth of Metal–Metal Oxide Nanostructures on Freestanding Graphene Paper for Flexible Biosensors

Flexible biosensors are of considerable current interest for the development of portable point‐of‐care medical products, minimally invasive implantable devices, and compact diagnostic platforms. A new type of flexible electrochemical sensor fabricated by depositing high‐density Pt nanoparticles on freestanding reduced graphene oxide paper (rGOP) carrying MnO₂ nanowire networks is reported. The triple‐component design offers new possibilities to integrate the mechanical and electrical properties of rGOP, the large surface area of MnO₂ networks, and the catalytic activity of well‐dispersed and small‐sized Pt nanoparticles prepared via ultrasonic‐electrodeposition. The sensitivity and selectivity that the flexible electrode demonstrates for nonenzymatic detection of H₂O₂ enables its use for monitoring H₂O₂ secretion by live cells. The strategy of structurally integrating metal, metal oxide, and graphene paper will provide new insight into the design of flexible electrodes for a wide range of applications in biosensing, bioelectronics, and lab‐on‐a‐chip devices.     

Laser Assisted Solution Synthesis of High Performance Graphene Supported Electrocatalysts

Simple, yet versatile, methods to functionalize graphene flakes with metal (oxide) nanoparticles are in demand, particularly for the development of advanced catalysts. Herein, based on light‐induced electrochemistry, a laser‐assisted, continuous, solution route for the simultaneous reduction and modification of graphene oxide with catalytic nanoparticles is reported. Electrochemical graphene oxide (EGO) is used as starting material and electron–hole pair source due to its low degree of oxidation, which imparts structural integrity and an ability to withstand photodegradation. Simply illuminating a solution stream containing EGO and metal salt (e.g., H₂PtCl₆ or RuCl₃) with a 248 nm wavelength laser produces reduced EGO (rEGO, oxygen content 4.0 at%) flakes, decorated with Pt (≈2.0 nm) or RuO₂ (≈2.8 nm) nanoparticles. The RuO₂–rEGO flakes exhibit superior catalytic activity for the oxygen evolution reaction, requiring a small overpotential of 225 mV to reach a current density of 10 mA cm^?2. The Pt–rEGO flakes (10.2 wt% of Pt) show enhanced mass activity for the hydrogen evolution reaction, and similar performance for oxygen reduction reaction compared to a commercial 20 wt% Pt/C catalyst. This simple production method is also used to deposit PtPd alloy and MnO_x nanoparticles on rEGO, demonstrating its versatility in synthesizing functional nanoparticle‐modified graphene materials.     

Electromagnetic characteristics of nanometer manganese dioxide composite materials

The electromagnetic properties of nanometer-sized manganese dioxide and silica dioxide/manganese dioxide composite in the frequency range 2–18 GHz are discussed in this paper. Findings show that MnO₂ is a kind of dielectric loss media with broad frequency bandwidth. Moreover, with the increasing of the MnO₂ filing proportion, the wave absorbing peak values drift to the lower frequency band. Analyses of transmission electron microscope (TEM) micrograph and electromagnetic parameters of MnO₂ particulate show that its wave attenuation property can be attributed mainly to its flaky and stripshaped topography and high dielectric constant.     

Nanocasting of Mesoporous In‐TM (TM = Co,Fe, Mn) Oxides: Towards 3D Diluted‐Oxide Magnetic Semiconductor Architectures

Transition metal (Co, Fe, Mn)‐doped In₂O_3?y mesoporous oxides are synthesized by nanocasting using mesoporous silica as hard templates. 3D ordered mesoporous replicas are obtained after silica removal in the case of the In‐Co and In‐Fe oxide powders. During the conversion of metal nitrates into the target mixed oxides, Co, Fe, and Mn ions enter the lattice of the In₂O₃ bixbyite phase via isovalent or heterovalent cation substitution, leading to a reduction in the cell parameter. In turn, non‐negligible amounts of oxygen vacancies are also present, as evidenced from Rietveld refinements of the X‐ray diffraction patterns. In addition to (In_1?xTM_x)₂O_3?y, minor amounts of Co₃O₄, α‐Fe₂O₃, and Mn_xO_y phases are also detected, which originate from the remaining TM cations not forming part of the bixbyite lattice. The resulting TM‐doped In₂O_3?y mesoporous materials show a ferromagnetic response at room temperature, superimposed on a paramagnetic background. Conversely, undoped In₂O_3?y exhibits a mixed diamagnetic‐ferromagnetic behavior with much smaller magnetization. The influence of the oxygen vacancies and the doping elements on the magnetic properties of these materials is discussed. Due to their 3D mesostructural geometrical arrangement and their room‐temperature ferromagnetic behavior, mesoporous oxide‐diluted magnetic semiconductors may become smart materials for the implementation of advanced components in spintronic nanodevices.     

Cd1–xMnxS Diluted Magnetic Semiconductors as Nanostructured Guest Species in Mesoporous Thin‐Film Silica Host Media

Recently, we demonstrated the possibility of synthesizing ordered nanowires of diluted magnetic II/VI semiconductors inside the channels of mesoporous silica host structures. Here, we expand this procedure from mesoporous powders to mesoporous thin films. Diluted magnetic semiconductors Cd_1–xMn_xS were synthesized within the pores of mesoporous thin‐film silica host structures by a wet‐impregnation technique using an aqueous solution of the respective metal acetates, followed by drying steps and a conversion to sulfide by thermal H₂S treatment. The presence of Cd_1–xMn_xS nanoparticles inside the pores was proved by powder X‐ray diffraction, infrared and Raman spectroscopy, and transmission electron microscopy. Photoluminescence excitation measurements clearly demonstrate the quantum size effect of the incorporated nanostructured guest species. The quality of the nanoparticles incorporated into the mesoporous films is comparable to that of those inside the mesoporous powders.     

Freely Tailorable Yolk-Shell Encapsulation: Versatile Applications in Ultralow-k Dielectric,Drug Delivery Systems,and Catalysts

Herein, a facile, controllable, and versatile method is reported to prepare monodisperse yolk-shell and yolk-multishell silica nanoparticles (NPs) with mesoporous shells by a novel selective etching strategy. The mechanism of selective etching based on fluoride-silica chemistry is investigated in detail and thus provides a fundamentally novel principle for the fabrication of yolk-shell NPs. Specifically, this unprecedented and versatile synthesis strategy can be used to encapsulate essentially any silica-based, carbon-based, metal, metal oxide, or other possible NPs. Noteworthy is that most of the yolk-shell mesoporous silica (mSiO₂) NPs are prepared for the first time. To demonstrate the major structural and compositional advantages of the designed yolk-shell NPs, their applications in the fields of ultralow-dielectric constant (k) materials, drug delivery systems, and catalysts were explored. In detail, the lowest k value of the prepared yolk-shellordered mesoporous silica@mSiO₂/fluorinated polybenzoxazole composite films is 2.02; The obtained yolk-shell mSiO₂/C@mSiO₂/C NPs possess high hydrophilicity and pH-responsive sensitivity; The conversion of the catalytic reaction of the designed magnetic yolk-shell hollow Fe₃O₄@SiO₂/Au@mSiO₂ NPs at 20 min is 97% with a high conversion rate (92%) and recyclability even after 10 reuses. This innovative work lays a solid foundation for freely tailorable yolk-shell encapsulation and will greatly stimulate more efforts devoted to relevant research and development.     

Ultrathin Cobalt–Manganese Nanosheets: An Efficient Platform for Enhanced Photoelectrochemical Water Oxidation with Electron‐Donating Effect

An ultrathin cobalt–manganese (Co‐Mn) nanosheet, consisting of amorphous Co(OH)_x layers and ultrasmall Mn₃O₄ nanocrystals, is designed as an efficient co‐catalyst on an α‐Fe₂O₃ film for photoelectrochemical (PEC) water oxidation. The uniformly distributed Co‐Mn nanosheets lead to a remarkable 2.6‐fold enhancement on the photocurrent density at 1.23 V versus reversible hydrogen electrode (RHE) and an impressive cathodic shift (≈200 mV) of onset potential compared with bare α‐Fe₂O₃ film. Furthermore, the decorated photoanode exhibits a prominent resistance against photocorrosion with excellent stability for over 10 h. Detailed mechanism investigation manifests that incorporation of Mn sites in the nanosheets could create electron donation to Co sites and facilitate the activation of the OH group, which drastically increases the catalytic activities for water oxidation. These findings provide valuable guidance for designing high‐performance co‐catalysts for PEC applications and open new avenues toward controlled fabrication of mixed metallic composites.