Bioactive Ion-Confined Ultracapacitive Memristors with Neuromorphic Functions.

The field of bioinspired iontronics, bridging electronic devices and ionic systems, has multiple biological applications. Carbon-based ultracapacitive devices hold promise for controlling bioactive ions via electric double layers due to their high-surface-area and biocompatible porous carbon electrodes. However, the interplay between complex bioactive ions and porous carbons remains unclear due to the variety of structures of bioactive ions present in biological systems. Herein, we investigate the adsorption behavior of a series of bioactive ammonium-based cations with varying alkyl chain lengths in nanoporous carbons. We find that strong physisorption results from the synergistic hydrophobic interaction and electrostatic attraction between porous carbons (with a negative zeta potential) and bioactive cations. Bioactive cations with varying alkyl chain lengths can be irreversibly physically adsorbed and confined within nanoporous carbons resulting in anion enrichment and depletion during electric polarization. This situation, in turn, results in a characteristic memristive behavior in all-carbon capacitive ionic memristor devices. Our findings highlight the relationship between the resistance state of the memristor and ion adsorption mechanisms in all-carbon capacitive devices, which hold potential for future transmitter delivery, biointerfacing, and neuromorphic devices.

Precursor-Derived Sensing Interdigitated Electrode Microstructures Based on Platinum and Nano Porous Carbon.

Interdigital electrodes were prepared using nanoimprint lithography and piezoelectric inkjet printing. These processes are simpler and more cost-effective than the industrially used electron beam lithography because of their purely mechanical process step. For the investigation of material dependence, platinum as well as carbon electrodes were fabricated. Afterwards electrodes with various line widths and spacings were tested for the application as a chemiresistive sensor for ferrocenyl-methanol and the influence of the gap-width and conductor cross-section on the sensitivity was investigated. The general suitability of the systems for the production of such structures could be confirmed. Structures with a limit of detection (LOD) down to 1.2 µM and 35.9 µM could be produced for carbon and platinum, respectively, as well as a response time of 3.6 s was achieved.

A Precursor-Derived Ultramicroporous Carbon for Printing Iontronic Logic Gates and Super-Varactors.

A liquid precursor for 3D printing ultramicroporous carbons (pore width <0.7 nm) to create a novel in-plane capacitive-analog of semiconductor-based diodes (CAPodes) is presented. This proof-of-concept integrates functional EDLCs into microstructured iontronic devices. The working principle is based on selective ion-sieving, controlling the size of the electrolyte ions, and the nanoporous sieving carbon's pore size. By blocking bulky electrolyte ions from entering the sub-nanometer pores, a unidirectional charging characteristic with controllable ion flux is achieved, leading to diodic U-I characteristics with a high rectification ratio. The liquid precursor approach enables successful printing of miniaturized in-plane CAPodes. A combination of inkjet and extrusion printing techniques with suitable inks is explored to fabricate electrode materials with engineered porosity. Deliberate fine-tuning of the ultramicroporous carbon's porosity and surface area is achieved using a customized carbon precursor and CO2 etching techniques. Electrochemical evaluation of the printed CAPodes demonstrates successful miniaturization compared with macroscopic film assembly. 3D manufacturing and miniaturization allow for the integration of CAPodes into logic gate circuits (OR, AND). For the first time, these switchable devices are used as variable capacitors in a high-pass filter application, adjusting the cut-off frequency of applied alternating voltage analogous to an I-MOS varactor.

General Design Concepts for CAPodes as Ionologic Devices.

Capacitive analogues of semiconductor diodes (CAPodes) present a new avenue for energy-efficient and nature-inspired next-generation computing devices. Here, we disclose the generalized concept for bias-direction-adjustable n- and p-CAPodes based on selective ion sieving. Controllable-unidirectional ion flux is realized by blocking electrolyte ions from entering sub-nanometer pores. The resulting CAPodes exhibit charge-storage characteristics with a high rectification ratio (96.29 %). The enhancement of capacitance is attributed to the high surface area and porosity of an omnisorbing carbon as counter electrode. Furthermore, we demonstrate the use of an integrated device in a logic gate circuit architecture to implement logic operations ('OR', 'AND'). This work demonstrates CAPodes as a generalized concept to achieve p-n and n-p analogue junctions based on selective ion electrosorption, provides a comprehensive understanding and highlights applications of ion-based diodes in ionologic architectures.

Bioactive Ion-Based Switchable Supercapacitors.

Switchable supercapacitors (SCs) enable a reversible electrically-driven uptake/release of bioactive ions by polarizing porous carbon electrodes. Herein we demonstrate the first example of a bioactive ion-based switchable supercapacitor. Based on choline chloride and porous carbons we unravel the mechanism of physisorption vs. electrosorption by nuclear magnetic resonance, Raman, and impedance spectroscopy. Weak physisorption facilitates electrically-driven electrolyte depletion enabling the controllable uptake/release of electrolyte ions. A new 4-terminal device is proposed, with a main capacitor and a detective capacitor for monitoring bioactive ion adsorption in situ. Ion-concentration control in printed choline-based switchable SCs realizes switching down to 8.3 % residual capacitance. The exploration of adsorption mechanisms in printable microdevices will open an avenue of manipulating bioactive ions for the application of drug delivery, neuromodulation, or neuromorphic devices.

Unraveling the Capacitive Charge Storage Mechanism of Nitrogen-Doped Porous Carbons by EQCM and ssNMR.

Fundamental understanding of ion electroadsorption processes in porous electrodes on a molecular level provides important guidelines for next-generation energy storage devices like electric double layer capacitors (EDLCs). Porous carbons functionalized by heteroatoms show enhanced capacitive performance, but the underlying mechanism is still elusive, due to the lack of reliable tools to precisely identify multiple N species and establish clear structure property relations. Here, we use advanced analytical techniques such as low-temperature solid-state NMR (ssNMR) and electrochemical quartz crystal microbalance (EQCM) to relate the complex nitrogen functionalities to the charging mechanisms and capacitive performance. For the first time, it is demonstrated at a molecular level that N-doping strongly influences the electroadsorption mechanism in EDLCs. Without N-doping, anion (SO42-) adsorption-desorption dominates the charging mechanism, whereas after doping, Li+ electroadsorption plays a key role. With the help of EQCM, it is demonstrated that SO42- is strongly immobilized on the N-doped surface, leaving Li+ as the main charge carrier. The smaller size and higher concentration of Li+ compared to SO42- benefit a higher capacitance. Amine/amide N is responsible for high capacitance, but surprisingly the pyridinic, pyrrolic, and graphitic N groups have no significant influence. 2D 1H-15N NMR spectroscopy indicates that the conversion from pyridinium to pyrrolic N gives rise to a slightly decreased capacitance. This work not only demonstrates ssNMR as a powerful tool for surface chemistry characterization of electrode materials but also uncovers the related charging mechanism by EQCM, paving the way toward a comprehensive picture of EDLC chemistry.

Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium-Sulfur Battery Cathodes.

Dithiine linkage formation via a dynamic and self-correcting nucleophilic aromatic substitution reaction enables the de novo synthesis of a porous thianthrene-based two-dimensional covalent organic framework (COF). For the first time, this organo-sulfur moiety is integrated as a structural building block into a crystalline layered COF. The structure of the new material deviates from the typical planar interlayer π-stacking of the COF to form undulated layers caused by bending along the C-S-C bridge, without loss of aromaticity and crystallinity of the overall COF structure. Comprehensive experimental and theoretical investigations of the COF and a model compound, featuring the thianthrene moiety, suggest partial delocalization of sulfur lone pair electrons over the aromatic backbone of the COF decreasing the band gap and promoting redox activity. Postsynthetic sulfurization allows for direct covalent attachment of polysulfides to the carbon backbone of the framework to afford a molecular-designed cathode material for lithium-sulfur (Li-S) batteries with a minimized polysulfide shuttle. The fabricated coin cell delivers nearly 77% of the initial capacity even after 500 charge-discharge cycles at 500 mA/g current density. This novel sulfur linkage in COF chemistry is an ideal structural motif for designing model materials for studying advanced electrode materials for Li-S batteries on a molecular level.

Green Precursors and Soft Templating for Printing Porous Carbon-Based Micro-supercapacitors.

A combination of soft lithographic printing and soft templating has been used to fabricate high-resolution interdigitated micro-supercapacitors (MSC). Surfactant-assisted self-assembly produces high surface area ordered mesoporous carbons (490 m2 g-1 ). For the first time, such precursors have been printed by nano-imprint lithography as microdevices with a line width of only 250 nm and a spacing of only 1 µm. The devices are crack-free with low specific resistance (1.2×10-5  Ωm) and show good device capacitance up to 0.21 F cm-3 .

Nanoimprint lithography of nanoporous carbon materials for micro-supercapacitor architectures.

Nanoimprint lithography is proposed as a highly versatile method for the production of nanostructured supercapacitors (micro-supercapacitors, MSC). Liquid sucrose- and lignin-precursor printing produces patterns with high quality and a line width down to 500 nm. The liquid-carbon-precursor NIL-printing approach enables nitrogen doping to achieve an increased supercapacitor performance for aqueous electrolytes (Li2SO4). The lines are interconverted into nanoporous carbon materials (d ≈ 1 nm) with high specific surface area (>1000 m2 g-1) to form stable structures reaching specific resistivities as low as ρ = 3.5 × 10-5 Ωm and capacitances up to 7 F cm-3.

Metal-Organic Framework/Graphene Quantum Dot Nanoparticles Used for Synergistic Chemo- and Photothermal Therapy.

In this study, a simple one-pot method was used to prepare a multifunctional platform for synergistic chemo- and photothermal therapy,, which is composed of zeolitic imidazolate framework-8 (ZIF-8) as drug nanocarriers and the embedded graphene quantum dots (GQDs) as local photothermal seeds. The structure, drug release behavior, photothermal effect, and synergistic therapeutic efficiency of the ZIF-8/GQD nanoparticles were systematically investigated. Using doxorubicin (DOX) as a model anticancer drug, the results showed that monodisperse ZIF-8/GQD nanoparticles with a particle size of 50-100 nm could encapsulate DOX during the synthesis procedure and trigger DOX release under acidic conditions. The DOX-loaded ZIF-8/GQD nanoparticles could efficiently convert near-infrared (NIR) irradiation into heat and thereby increase the temperature. More importantly, with breast cancer 4T1 cells as a model cellular system, the results indicated that the combined chemo- and photothermal therapy with DOX-ZIF-8/GQD nanoparticles exhibited a significant synergistic effect, resulting in a higher efficacy to kill cancer cells compared with chemotherapy and photothermal therapy alone. Hence, ZIF-8/GQD nanoparticles would be promising as versatile nanocarriers for synergistic cancer therapy.

Graphene Quantum Dots-Capped Magnetic Mesoporous Silica Nanoparticles as a Multifunctional Platform for Controlled Drug Delivery, Magnetic Hyperthermia, and Photothermal Therapy.

A multifunctional platform is reported for synergistic therapy with controlled drug release, magnetic hyperthermia, and photothermal therapy, which is composed of graphene quantum dots (GQDs) as caps and local photothermal generators and magnetic mesoporous silica nanoparticles (MMSN) as drug carriers and magnetic thermoseeds. The structure, drug release behavior, magnetic hyperthermia capacity, photothermal effect, and synergistic therapeutic efficiency of the MMSN/GQDs nanoparticles are investigated. The results show that monodisperse MMSN/GQDs nanoparticles with the particle size of 100 nm can load doxorubicin (DOX) and trigger DOX release by low pH environment. Furthermore, the MMSN/GQDs nanoparticles can efficiently generate heat to the hyperthermia temperature under an alternating magnetic field or by near infrared irradiation. More importantly, breast cancer 4T1 cells as a model cellular system, the results indicate that compared with chemotherapy, magnetic hyperthermia or photothermal therapy alone, the combined chemo-magnetic hyperthermia therapy or chemo-photothermal therapy with the DOX-loaded MMSN/GQDs nanosystem exhibits a significant synergistic effect, resulting in a higher efficacy to kill cancer cells. Therefore, the MMSN/GQDs multifunctional platform has great potential in cancer therapy for enhancing the therapeutic efficiency.

High Area Capacity Lithium-Sulfur Full-cell Battery with Prelitiathed Silicon Nanowire-Carbon Anodes for Long Cycling Stability.

We show full Li/S cells with the use of balanced and high capacity electrodes to address high power electro-mobile applications. The anode is made of an assembly comprising of silicon nanowires as active material densely and conformally grown on a 3D carbon mesh as a light-weight current collector, offering extremely high areal capacity for reversible Li storage of up to 9 mAh/cm(2). The dense growth is guaranteed by a versatile Au precursor developed for homogenous Au layer deposition on 3D substrates. In contrast to metallic Li, the presented system exhibits superior characteristics as an anode in Li/S batteries such as safe operation, long cycle life and easy handling. These anodes are combined with high area density S/C composite cathodes into a Li/S full-cell with an ether- and lithium triflate-based electrolyte for high ionic conductivity. The result is a highly cyclable full-cell with an areal capacity of 2.3 mAh/cm(2), a cyclability surpassing 450 cycles and capacity retention of 80% after 150 cycles (capacity loss <0.4% per cycle). A detailed physical and electrochemical investigation of the SiNW Li/S full-cell including in-operando synchrotron X-ray diffraction measurements reveals that the lower degradation is due to a lower self-reduction of polysulfides after continuous charging/discharging.

Crystallographic insights into (CH3NH3)3(Bi2I9): a new lead-free hybrid organic-inorganic material as a potential absorber for photovoltaics.

The crystal structure of a new bismuth-based light-absorbing material for the application in solar cells was determined by single crystal X-ray diffraction for the first time. (CH3NH3)3(Bi2I9) (MBI) is a promising alternative to recently rapidly progressing hybrid organic-inorganic perovskites due to the higher tolerance against water and low toxicity. Single crystal X-ray diffraction provides detailed structural information as an essential prerequisite to gain a fundamental understanding of structure property relationships, while powder diffraction studies demonstrate a high degree of crystallinity in thin films.

Biological Chitin-MOF Composites with Hierarchical Pore Systems for Air-Filtration Applications.

Metal-organic frameworks (MOFs) are promising materials for gas-separation and air-filtration applications. However, for these applications, MOF crystallites need to be incorporated in robust and manageable support materials. We used chitin-based networks from a marine sponge as a non-toxic, biodegradable, and low-weight support material for MOF deposition. The structural properties of the material favor predominant nucleation of the MOF crystallites at the inside of the hollow fibers. This composite has a hierarchical pore system with surface areas up to 800 m(2) g(-1) and pore volumes of 3.6 cm(3) g(-1) , allowing good transport kinetics and a very high loading of the active material. Ammonia break-through experiments highlight the accessibility of the MOF crystallites and the adsorption potential of the composite indicating their high potential for filtration applications for toxic industrial gases.

Few-layer graphene shells and nonmagnetic encapsulates: a versatile and nontoxic carbon nanomaterial.

In this work a simple and scalable approach to coat nonmagnetic nanoparticles with few-layer graphene is presented. In addition, the easy processing of such nanoparticles to remove their core, leaving only the 3D graphene nanoshell, is demonstrated. The samples are comprehensively characterized, as are their versatility in terms of functionalization and as a material for electrochemical storage. Indeed, these 3D graphene nanostructures are easily functionalized much as is found with carbon nanotubes and planar graphene. Electrochemical investigations indicate these nanostructures are promising for stable long-life battery applications. Finally, initial toxicological investigations suggest no acute health risk from these 3D graphene nanostructures.

Metal deposition by electroless plating on polydopamine functionalized micro- and nanoparticles.

A novel approach for the fabrication of metal coated micro- and nanoparticles by functionalization with a thin polydopamine layer followed by electroless plating is reported. The particles are initially coated with polydopamine via self-polymerization. The resulting polydopamine coated particles have a surface rich in catechols and amino groups, resulting in a high affinity toward metal ions. Thus, they provide an effective platform for selective electroless metal deposition without further activation and sensitization steps. The combination of a polydopamine-based functionalization with electroless plating ensures a simple, scalable, and cost-effective metal coating strategy. Silver-plated tungsten carbide microparticles, copper-plated tungsten carbide microparticles, and copper-plated alumina nanoparticles were successfully fabricated, showing also the high versatility of the method, since the polymerization of dopamine leads to the formation of an adherent polydopamine layer on the surface of particles of any material and size. The metal coated particles produced with this process are particularly well suited for the production of metal matrix composites, since the metal coating increases the wettability of the particles by the metal, promoting their integration within the matrix. Such composite materials are used in a variety of applications including electrical contacts, components for the automotive industries, magnets, and electromagnetic interference shielding.