Enhanced Thermoelectric Properties of Ti2CO2-Bismuthene-Ti2CO2: Optimized Power Factor and Reduced Thermal Conductivity.

In this study, bismuthene was intercalated between bilayer Ti2CTx to induce significant modifications in its electronic and phonon structures, thereby enhancing its thermoelectric properties. First-principles calculations reveal that the insertion of bismuthene transforms the Ti2CO2 system from a semiconductor into a metal and optimizes the thermoelectric properties of bilayer Ti2CO2 by enhancing its power factor and reducing its lattice thermal conductivity. Under the first-principles calculation parameters used in this study, the ZT of the Ti2CO2 system increased from 0.12 to 0.55. Conversely, for metallic bilayer MXenes, the introduction of bismuthene led to a substantial decrease in ZT (from 0.53 to 0.11 in the Ti2C system and from 0.07 to 0.05 in the Ti2CCl2 system). This study investigates the physical mechanisms underlying the enhancement of thermoelectric properties from both electronic and phononic perspectives and provides theoretical insights into the development and application of MXene-based thermoelectric materials.

Enhanced Nonradiative Charge Recombination in Microfiber-Based Bismuthene.

After the first report of a graphene-based passive mode-locking ultrafast fiber laser, two-dimensional materials as efficient saturable absorbers offer a new horizon in ultrafast fiber laser. However, the interactions on atomic scale between these two-dimensional materials and fiber and the fiber effect on the carrier dynamics have not been realized. To figure out the exact role of fiber and the carrier dynamics affected by the fiber substrate related to ultrafast photonics, bismuthene, a newly reported 2D quantum material used in a passive mode-locking fiber laser, deposited on α-quartz has been investigated. We surprisingly found that the α-quartz substrate can strongly accelerate the nonradiative electron-hole recombination of bismuthene in theory, and the transient absorption spectra of bismuthene on normal glass and α-quartz further verify the substrate effect on carrier dynamics of bismuthene. The discovery provides new thinking about substrate effect to regulate the performance of ultrafast mode-locking fiber lasers as well as ultrafast photonics.

Synovium microenvironment-responsive injectable hydrogel inducing modulation of macrophages and elimination of synovial fibroblasts for enhanced treatment of rheumatoid arthritis.

Rheumatoid arthritis (RA) is a progressive autoimmune disease accompanied by joint swelling, cartilage erosion and bone damage. Drug therapy for RA has been restricted due to poor therapeutic effect, recurrence and adverse effects. Macrophages and synovial fibroblasts both play important roles in the pathology of RA. Macrophages secrete large amount of pro-inflammatory cytokines, while synovial fibroblasts are tightly correlated with hypoxia synovium microenvironment, cytokine release, recruitment of pro-inflammatory cells, bone and cartilage erosion. Therefore, in this timely research, an injectable and pH-sensitive peptide hydrogel loading methotrexate (MTX) and bismuthene nanosheet/polyethyleneimine (BiNS/PEI) has been developed to reduce the activity of macrophages and eliminate over-proliferated synovial fibroblasts simultaneously. MTX can reduce the cytokine secretion of macrophages/anti-apoptosis property of synovial fibroblasts and BiNS/PEI can eliminate synovial fibroblasts via photodynamic therapy (PDT) and photothermal therapy (PTT) routes. The hydrogel was injected into the acidic inflammatory synovium for precise targeting and served as a drug reservoir for pH responsive and sustained drug release, while improving the bioavailability and reducing the toxicity of MTX. Excellent therapeutic efficacy has been achieved in both in vivo and in vitro studies, and this unique drug delivery system provides a new and robust strategy to eliminate synovial fibroblasts and modulate immune system for RA treatment in clinical.

Sandwiched Epitaxy Growth of 2D Single-Crystalline Hexagonal Bismuthene Nanoflakes for Electrocatalytic CO2 Reduction.

Two-dimensional (2D) bismuthene is predicted to possess intriguing physical properties, but its preparation remains challenging due to the high surface energy constraint. Herein, we report a sandwiched epitaxy growth strategy for the controllable preparation of 2D bismuthene between a Cu foil substrate and a h-BN covering layer. The top h-BN layer plays a crucial role in suppressing the structural transformation of bismuthene and compensating for the charge transfer from the bismuthene to the Cu(111) surface. The bismuthene nanoflakes present a superior thermal stability up to 500 °C in air, attributed to the passivation effect of the h-BN layer. Moreover, the bismuthene nanoflakes demonstrate an ultrahigh faradaic efficiency of 96.3% for formate production in the electrochemical CO2 reduction reaction, which is among the highest reported for Bi-based electrocatalysts. This study offers a promising approach to simultaneously synthesize and protect 2D bismuthene nanoflakes, which can be extended to other 2D materials with a high surface energy.

Ultrafast Momentum-Resolved Hot Electron Dynamics in the Two-Dimensional Topological Insulator Bismuthene.

Two-dimensional quantum spin Hall (QSH) insulators are a promising material class for spintronic applications based on topologically protected spin currents in their edges. Yet, they have not lived up to their technological potential, as experimental realizations are scarce and limited to cryogenic temperatures. These constraints have also severely restricted characterization of their dynamical properties. Here, we report on the electron dynamics of the novel room-temperature QSH candidate bismuthene after photoexcitation using time- and angle-resolved photoemission spectroscopy. We map the transiently occupied conduction band and track the full relaxation pathway of hot photocarriers. Intriguingly, we observe photocarrier lifetimes much shorter than those in conventional semiconductors. This is ascribed to the presence of topological in-gap states already established by local probes. Indeed, we find spectral signatures consistent with these earlier findings. Demonstration of the large band gap and the view into photoelectron dynamics mark a critical step toward optical control of QSH functionalities.

Covalent Functionalization of Antimonene and Bismuthene Nanosheets.

Antimonene and bismuthene are promising members of the 2D pnictogen family with their tunable band gaps, high electronic conductivity, and ambient stability, making them suitable for electronic and optoelectronic applications. However, semi-metal to semiconductor transition occurs only in the mono/bilayer regime, limiting their applications. Covalent functionalization is a versatile method for tuning materials' chemical, electronic, and optical properties and can be explored for tuning the properties of pnictogens. In this work, emissions in liquid exfoliated antimonene and bismuthene are observed at ≈2.23 and ≈2.33 eV, respectively. Covalent functionalization of antimonene and bismuthene with p-nitrobenzene diazonium salt proceeds with the transfer of lone pairs from Sb/Bi to the diazonium salt, introducing organic moieties on the surface attached predominantly via Sb/BiC bonds. Consequently, Sb/Bi signatures in Raman and X-ray photoelectron spectra are blue-shifted, implying lattice distortion and charge transfer. Interestingly, emission can be tailored upon functionalization to 2.18 and 2.27 eV for antimonene and bismuthene respectively, and this opens the possibility of tuning the properties of pnictogens and related materials. This is the first report on covalent functionalization of antimonene and bismuthene. It sheds light on the reaction mechanism on pnictogen surfaces and demonstrates tunability of optical property and surface passivation.

Ultrathin epitaxial Bi film growth on 2D HfTe2template.

Among ultrathin monoelemental two-dimensional (2D) materials, bismuthene, the single layer of heavier group-VΑ element bismuth (Bi), has been predicted to have large non trivial gap. Here, we demonstrate the growth of Bi films by molecular beam epitaxy on 2D-HfTe2template. At the initial stage of Bi deposition (1-2 bilayers, BL), both the pseudocubic Bi(110) and the hexagonal Bi(111) phases are formed. When reaching 3 BL Bi, a transformation to pure hexagonal Bi(111) occurs. The electronic band structure of 3 BL Bi(111) films was measured by angle-resolved photoemission spectroscopy showing very good matching with the density functional theory band structure calculations of 3 BL free standing Bi(111). The grown Bi(111) thin film was capped with a protective Al2O3layer and its stability under ambient conditions, necessary for practical applications and device fabrication, was confirmed by x-ray photoelectron spectroscopy and Raman spectroscopy.

Bismuthene Metallurgy: Transformation of Bismuth Particles to Ultrahigh-Aspect-Ratio 2D Microsheets.

Ultrathin bismuth exhibits promising performance for topological insulators due to its narrow band gap and intrinsic strong spin-orbit coupling, as well as for energy-related applications because of its electronic and mechanical properties. However, large-scale production of 2D sheets via liquid-phase exfoliation as an established large-scale method is restricted by the strong interaction between bismuth layers. Here, a sonication method is utilized to produce ultrahigh-aspect-ratio bismuthene microsheets. The studies on the mechanism excludes the exfoliation of the layered bulk bismuth and formation of the microsheets is attributed to the melting of spherical particles (r = 1.5 µm) at a high temperature-generated under the ultrasonic tip-followed by a recrystallization step producing uniformly-shaped ultrathin microsheets (A = 0.5-2 µm2 , t: ≈2 nm). Notably, although the preparation is performed in oxygenated aqueous solution, the sheets are not oxidized, and they are stable under ambient conditions for at least 1 month. The microsheets are used to construct a vapor sensor using electrochemical impedance spectroscopy as detection technique. The device is highly selective, and it shows long-term stability. Overall, this project exhibits a reproducible method for large-scale preparation of ultrathin bismuthene microsheets in a benign environment, demonstrating opportunities to realize devices based on bismuthene.

Toward Realistic Amorphous Topological Insulators.

The topological properties of materials are, until now, associated with the features of their crystalline structure, although translational symmetry is not an explicit requirement of the topological phases. Recent studies of hopping models on random lattices have demonstrated that amorphous model systems show a nontrivial topology. Using ab initio calculations, we show that two-dimensional amorphous materials can also display topological insulator properties. More specifically, we present a realistic state-of-the-art study of the electronic and transport properties of amorphous bismuthene systems, showing that these materials are topological insulators. These systems are characterized by the topological index [Formula: see text]2 = 1 and bulk-edge duality, and their linear conductance is quantized, [Formula: see text], for Fermi energies within the topological gap. Our study opens the path to the experimental and theoretical investigation of amorphous topological insulator materials.

Ultrathin Bismuth Nanosheets for Stable Na-Ion Batteries: Clarification of Structure and Phase Transition by in Situ Observation.

Bismuth has garnered tremendous interest for Na-ion batteries (NIBs) due to potentially high volumetric capacity. Yet, the bismuth upon sodiation/desodiation experiencing structure and phase transitions remains unclear, which sets a challenge for accessing nanotechnology and nanofabrication to achieve its applicability. Here, we use in situ transmission electron microscopy to disclose the structure and phase transitions of layered bismuth (few-layer bismuth nanosheets) during Na+ intercalation and alloying processes. Multistep phase transitions from Bi → NaBi → c-Na3Bi (cubic) → h-Na3Bi (hexagonal) are clearly identified, during which the Na+ migration from interlayer to in-plane evokes the structure transition from ABCABC stacking type of c-Na3Bi to ABABAB stacking type of h-Na3Bi. It is found that the metastable c-Na3Bi devotes to buffer the dramatic structure changes from thermodynamic stable h-Na3Bi, which unveils the origin of volume expansion for bismuth and has important consequences for 2D in-plane structure. As the lateral ductility can efficiently alleviate the in-plane mechanical strain caused by the Na+ migration, the few-layer bismuth nanosheet exhibits a potential cyclability for NIBs. Our findings will encourage more attention to bismuthene as a novel anode material for secondary batteries.

Metal-Organic Layers Leading to Atomically Thin Bismuthene for Efficient Carbon Dioxide Electroreduction to Liquid Fuel.

Electrochemical reduction of CO2 to valuable fuels is appealing for CO2 fixation and energy storage. However, the development of electrocatalysts with high activity and selectivity in a wide potential window is challenging. Herein, atomically thin bismuthene (Bi-ene) is pioneeringly obtained by an in situ electrochemical transformation from ultrathin bismuth-based metal-organic layers. The few-layer Bi-ene, which possesses a great mass of exposed active sites with high intrinsic activity, has a high selectivity (ca. 100 %), large partial current density, and quite good stability in a potential window exceeding 0.35 V toward formate production. It even deliver current densities that exceed 300.0 mA cm-2 without compromising selectivity in a flow-cell reactor. Using in situ ATR-IR spectra and DFT analysis, a reaction mechanism involving HCO3 - for formate generation was unveiled, which brings new fundamental understanding of CO2 reduction.

Semimetallic Bismuthene with Edge-Rich Dangling Bonds: Broad-Spectrum-Driven and Edge-Confined Electron Enhancement Boosting CO2 Hydrogenation Reduction.

Broad-spectrum-driven high-performance artificial photosynthesis is quite challenging. Herein, atomically ultrathin bismuthene with semimetallic properties is designed and demonstrated for broad-spectrum (ultraviolet-visible-near infrared light) (UV-vis-NIR)-driven photocatalytic CO2 hydrogenation. The trap states in the bandgap produced by edge dangling bonds prolong the lifetime of the photogenerated electrons from 90 ps in bulk Bi to 1650 ps in bismuthine, and excited-state electrons are enriched at the edge of bismuthine. The edge dangling bonds of bismuthene as the active sites for adsorption/activation of CO2 increase the hybridization ability of the Bi 6p orbital and O 2p orbital to significantly reduce the catalytic reaction energy barrier and promote the formation of C─H bonds until the generation of CH4. Under λ ≥ 400 nm and λ ≥ 550 nm irradiation, the utilization ratios of photogenerated electron reduction CO2 hydrogenation to CO and CH4 for bismuthene are 58.24 and 300.50 times higher than those of bulk Bi, respectively. Moreover, bismuthene can extend the CO2 hydrogenation reaction to the near-infrared region (λ ≥ 700 nm). This pioneering work employs the single semimetal element as an artificial photosynthetic catalyst to produce a broad spectral response.

Free PCR virus detection via few-layer bismuthene and tetrahedral DNA nanostructured assemblies.

In this work we describe a highly sensitive method based on a biocatalyzed electrochemiluminescence approach. The system combines, for the first time, the use of few-layer bismuthene (FLB) as a platform for the oriented immobilization of tetrahedral DNA nanostructures (TDNs) specifically designed and synthetized to detect a specific SARS-CoV-2 gene sequence. In one of its vertices, these TDNs contain a DNA capture probe of the open reading frame 1 ab (ORF1ab) of the virus, available for the biorecognition of the target DNA/RNA. At the other three vertices, there are thiol groups that enable the stable anchoring/binding to the FLB surface. This novel geometry/approach enables not only the binding of the TDNs to surfaces, but also the orientation of the capture probe in a direction normal to the bismuthine surface so that it is readily accessible for binding/recognition of the specific SARS-CoV-2 sequence. The analytical signal is based on the anodic electrochemiluminescence (ECL) intensity of luminol which, in turn, arises as a result of the reaction with H2O2, generated by the enzymatic reaction of glucose oxidation, catalyzed by the biocatalytic label avidin-glucose oxidase conjugate (Av-GOx), which acts as co-reactant in the electrochemiluminescent reaction. The method exhibits a limit of detection (LOD) of 4.31 aM and a wide linear range from 14.4 aM to 1.00 µM, and its applicability was confirmed by detecting SARS-CoV-2 in nasopharyngeal samples from COVID-19 patients without the need of any amplification process.

Microenvironment Responsive Hydrogel Exerting Inhibition of Cascade Immune Activation and Elimination of Synovial Fibroblasts for Rheumatoid Arthritis Therapy.

Rheumatoid arthritis (RA) is a progressive autoimmune disease and drug therapy has been restricted due to poor therapeutic efficacy and adverse effects. In RA synovium, dendritic cells present self-antigens to activate cascade immune pathway. Furthermore, downstream macrophages secrete high levels of pro-inflammatory cytokines; Hyperplasia of activated synovial fibroblasts (FLS) is responsible for hypoxic synovium microenvironment, secretion of cytokines/chemokines and erosion of bone/cartilage tissues. Positive feedback loop of inflammation between macrophages and FLS independent of antigen-presentation is constructed. Herein, an injectable pH-sensitive peptide hydrogel encapsulating siRNA/Methotrexate-polyethyleneimine (siMP, including sip65MP, sip38MP, siCD86MP) and Bismuthene nanosheet/Methotrexate-polyethyleneimine (BiMP) is successfully developed. Among them, siCD86MP reduces protein level of co-stimulatory molecule CD86 while sip65MP and sip38MP separately inhibit NF-κB and MAPK-p38 pathways of macrophages and FLS to suppress secretion of cytokines and MMPs. Meanwhile, reduction in anti-apoptotic property of FLS induced by inhibition of NF-κB pathway has a synergistic effect with photodynamic therapy (PDT) and photothermal therapy (PTT) mediated by BiMP for FLS elimination, effectively ameliorating hypoxic synovium microenvironment. After being injected into synovium, hydrogel responds to acidic microenvironment and serves as a reservoir for sustained drug release and inherent retention capacity of which enables cationic nanoparticles to bypass tissue barrier for precise synovium targeting. This brand-new drug delivery system combines modulating cascade immune pathway from beginning to end by RNAi and eliminating FLS for improving synovium microenvironment by phototherapy together, providing a robust strategy for clinical RA treatment.

Bismuthene - Tetrahedral DNA nanobioconjugate for virus detection.

In this work, we present an electrochemical sensor for fast, low-cost, and easy detection of the SARS-CoV-2 spike protein in infected patients. The sensor is based on a selected combination of nanomaterials with a specific purpose. A bioconjugate formed by Few-layer bismuthene nanosheets (FLB) and tetrahedral DNA nanostructures (TDNs) is immobilized on Carbon Screen-Printed Electrodes (CSPE). The TDNs contain on the top vertex an aptamer that specifically binds to the SARS-CoV-2 spike protein, and a thiol group at the three basal vertices to anchor to the FLB. The TDNs are also marked with a redox indicator, Azure A (AA), which allows the direct detection of SARS-CoV-2 spike protein through changes in the current intensity of its electrolysis before and after the biorecognition reaction. The developed sensor can detect SARS-CoV-2 spike protein with a detection limit of 1.74 fg mL-1 directly in nasopharyngeal swab human samples. Therefore, this study offers a new strategy for rapid virus detection since it is versatile enough for different viruses and pathogens.

Synergized photothermal therapy and magnetic field induced hyperthermia via bismuthene for lung cancer combinatorial treatment.

Thanks to its intrinsic properties, two-dimensional (2D) bismuth (bismuthene) can serve as a multimodal nanotherapeutic agent for lung cancer acting through multiple mechanisms, including photothermal therapy (PTT), magnetic field-induced hyperthermia (MH), immunogenic cell death (ICD), and ferroptosis. To investigate this possibility, we synthesized bismuthene from the exfoliation of 3D layered bismuth, prepared through a facile method that we developed involving surfactant-assisted chemical reduction, with a specific focus on improving its magnetic properties. The bismuthene nanosheets showed high in vitro and in vivo anti-cancer activity after simultaneous light and magnetic field exposure in lung adenocarcinoma cells. Only when light and magnetic field are applied together, we can achieve the highest anti-cancer activity compared to the single treatment groups. We have further shown that ICD-dependent mechanisms were involved during this combinatorial treatment strategy. Beyond ICD, bismuthene-based PTT and MH also resulted in an increase in ferroptosis mechanisms both in vitro and in vivo, in addition to apoptotic pathways. Finally, hemolysis in human whole blood and a wide variety of assays in human peripheral blood mononuclear cells indicated that the bismuthene nanosheets were biocompatible and did not alter immune function. These results showed that bismuthene has the potential to serve as a biocompatible platform that can arm multiple therapeutic approaches against lung cancer.

Interfacial assembled porous bismuthene/Ti3C2Tx MXene heterostructure for highly efficient capacitive deionization.

Capacitive deionization (CDI) is perceived as a promising technology for freshwater production owing to its environmentally friendly nature and low energy consumption. To date, the development of high-performance electrode materials represents the foremost challenge for CDI technology. In this work, the porous bismuthene/MXene (P-Bi-ene/MXene) heterostructure was synthesized using a simple interfacial self-assembly method with two-dimensional (2D) bismuthene and Ti3C2Tx MXene. Within the P-Bi-ene/MXene heterostructure, the porous structure can increase the active site and facilitate ion transport. Simultaneously, MXene effectively enhances the conductivity of the heterostructure, resulting in accelerating electron transport. Due to these attributes, the P-Bi-ene/MXene heterostructure demonstrates high desalination capacity (90.0 mg/g), fast desalination rate, and good cycling performance. The simple self-assembly strategy between 2D/2D materials described herein may offer inspirations for the synthesis of innovative electrode materials with high performance.

Sodium-borohydride exfoliated bismuthene loaded with Mitomycin C for chemo-photo-radiotherapy of triple negative breast cancer.

In current study, a new remotely controlled drug delivery, radio-sensitizing, and photothermal therapy agent based on thioglycolic acid modified bismuth nanosheets is thoroughly evaluated. Bismuth nanosheets were synthesized using sodium borohydride (NaBH4) and Tween 20 through low energy (400 W) sonication within 2 h. The resultant nanosheets were 40-60 nm in size and 1-3 atomic layers in thickness. The morphological and structural characteristics of the nanosheets were studied using transmission electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, Raman spectroscopy and ultraviolet spectroscopy. The surface of the nanosheets was modified using thioglycolic acid, which resulted in enhanced Mitomycin C loading capacity to 274.35% and circumvented the burst drug release due to the improved electrostatic interactions. At pH 7.4 and 5.0, the drug release was significantly boosted from 45.1 to 69.8%, respectively. Thioglycolic acid modified bismuth nanosheets under 1064 nm laser irradiation possessed photothermal conversion efficiency of η=51.4% enabling a temperature rise of 24.9 °C at 100 µg/ml in 5 min. The combination of drug delivery, photothermal therapy, and radio-sensitization greatly damaged the MDA-MB-231 cells through apoptosis and diminished their colony forming.

A 2D Bismuth-Induced Honeycomb Surface Structure on GaAs(111).

Two-dimensional (2D) topological insulators have fascinating physical properties which are promising for applications within spintronics. In order to realize spintronic devices working at room temperature, materials with a large nontrivial gap are needed. Bismuthene, a 2D layer of Bi atoms in a honeycomb structure, has recently attracted strong attention because of its record-large nontrivial gap, which is due to the strong spin-orbit coupling of Bi and the unusually strong interaction of the Bi atoms with the surface atoms of the substrate underneath. It would be a significant step forward to be able to form 2D materials with properties such as bismuthene on semiconductors such as GaAs, which has a band gap size relevant for electronics and a direct band gap for optical applications. Here, we present the successful formation of a 2D Bi honeycomb structure on GaAs, which fulfills these conditions. Bi atoms have been incorporated into a clean GaAs(111) surface, with As termination, based on Bi deposition under optimized growth conditions. Low-temperature scanning tunneling microscopy and spectroscopy (LT-STM/S) demonstrates a well-ordered large-scale honeycomb structure, consisting of Bi atoms in a √3 × âˆš3 30° reconstruction on GaAs(111). X-ray photoelectron spectroscopy shows that the Bi atoms of the honeycomb structure only bond to the underlying As atoms. This is supported by calculations based on density functional theory that confirm the honeycomb structure with a large Bi-As binding energy and predict Bi-induced electronic bands within the GaAs band gap that open up a gap of nontrivial topological nature. STS results support the existence of Bi-induced states within the GaAs band gap. The GaAs:Bi honeycomb layer found here has a similar structure as previously published bismuthene on SiC or on Ag, though with a significantly larger lattice constant and only weak Bi-Bi bonding. It can therefore be considered as an extreme case of bismuthene, which is fundamentally interesting. Furthermore, it has the same exciting electronic properties, opening a large nontrivial gap, which is the requirement for room-temperature spintronic applications, and it is directly integrated in GaAs, a direct band gap semiconductor with a large range of (opto)electronic devices.

Vertically Aligned Bismuthene Nanosheets on MXene for High-Performance Capacitive Deionization.

Capacitive deionization has been considered as a promising solution to the challenge of freshwater shortage due to its high efficiency, low environmental footprint, and low energy consumption. However, developing advanced electrode materials to improve capacitive deionization performance remains a challenge. Herein, the hierarchical bismuthene nanosheets (Bi-ene NSs)@MXene heterostructure was successfully prepared by combining the Lewis acidic molten salt etching and the galvanic replacement reaction, which achieves the effective utilization of the molten salt etching byproducts (residual copper). The vertically aligned bismuthene nanosheets array evenly in situ grown on the surface of MXene, which not only facilitate ion and electron transport as well as offer abundant active sites but also provide strong interfacial interaction between bismuthene and MXene. Benefiting from the above advantages, the Bi-ene NSs@MXene heterostructure as a promising capacitive deionization electrode material exhibits high desalination capacity (88.2 mg/g at 1.2 V), fast desalination rate, and good long-term cycling performance. Moreover, the mechanisms involved were elaborated by systematical characterizations and density functional theory calculations. This work provides inspirations for the preparation of MXene-based heterostructures and their application for capacitive deionization.