Control of Neuronal Survival and Development Using Conductive Diamond.

This study demonstrates the control of neuronal survival and development using nitrogen-doped ultrananocrystalline diamond (N-UNCD). We highlight the role of N-UNCD in regulating neuronal activity via near-infrared illumination, demonstrating the generation of stable photocurrents that enhance neuronal survival and neurite outgrowth and foster a more active, synchronized neuronal network. Whole transcriptome RNA sequencing reveals that diamond substrates improve cellular-substrate interaction by upregulating extracellular matrix and gap junction-related genes. Our findings underscore the potential of conductive diamond as a robust and biocompatible platform for noninvasive and effective neural tissue engineering.

Diamond Supercapacitors: Towards Durable, Safe, and Biocompatible Aqueous-Based Energy Storage.

Durable and safe energy storage is required for the next generation of miniature bioelectronic devices, in which aqueous electrolytes are preferred due to the advantages in safety, low cost, and high conductivity. While rechargeable aqueous batteries are among the primary choices with relatively low power requirements, their lifetime is generally limited to a few thousand charging/discharging cycles as the electrode material can degrade due to electrochemical reactions. Electrical double layer capacitors (EDLCs) possess increased cycling stability and power density, although with as-yet lower energy density, due to quick electrical adsorption and desorption of ions without involving chemical reactions. However, in aqueous solution, chemical reactions which cause electrode degradation and produce hazardous species can occur when the voltage is increased beyond its operation window to improve the energy density. Diamond is a durable and biocompatible electrode material for supercapacitors, while at the same time provides a larger voltage window in biological environments. For applications requiring higher energy density, diamond-based pseudocapacitors (PCs) have also been developed, which combine EDLCs with fast electrochemical reactions. Here we inspect the properties of diamond-related materials and discuss their advantages and disadvantages when used as EDLC and PC materials. We argue that further optimization of the diamond surface chemistry and morphology, guided by computational modelling of the interface, can lead to supercapacitors with enhanced performance. We envisage that such diamond-based supercapacitors could be used in a wide range of applications and in particular those requiring high performance in biomedical applications.

Self-Assembly of Ir-Based Nanosheets with Ordered Interlayer Space for Enhanced Electrocatalytic Water Oxidation.

Iridium (Ir)-based electrocatalysts are widely explored as benchmarks for acidic oxygen evolution reactions (OERs). However, further enhancing their catalytic activity remains challenging due to the difficulty in identifying active species and unfavorable architectures. In this work, we synthesized ultrathin Ir-IrOx/C nanosheets with ordered interlayer space for enhanced OER by a nanoconfined self-assembly strategy, employing block copolymer formed stable end-merged lamellar micelles. The interlayer distance of the prepared Ir-IrOx/C nanosheets was well controlled at ∼20 nm and Ir-IrOx nanoparticles (∼2 nm) were uniformly distributed within the nanosheets. Importantly, the fabricated Ir-IrOx/C electrocatalysts display one of the lowest overpotential (η) of 198 mV at 10 mA cm-2geo during OER in an acid medium, benefiting from their features of mixed-valence states, rich electrophilic oxygen species (O(II-δ)-), and favorable mesostructured architectures. Both experimental and computational results reveal that the mixed valence and O(II-δ)- moieties of the 2D mesoporous Ir-IrOx/C catalysts with a shortened Ir-O(II-δ)- bond (1.91 Å) is the key active species for the enhancement of OER by balancing the adsorption free energy of oxygen-containing intermediates. This strategy thus opens an avenue for designing high performance 2D ordered mesoporous electrocatalysts through a nanoconfined self-assembly strategy for water oxidation and beyond.

Electrolyte gating in graphene-based supercapacitors and its use for probing nanoconfined charging dynamics.

Graphene-based nanoporous materials have been extensively explored as high-capacity ion electrosorption electrodes for supercapacitors. However, little attention has been paid to exploiting the interactions between electrons that reside in the graphene lattice and the ions adsorbed between the individual graphene sheets. Here we report that the electronic conductance of a multilayered reduced graphene oxide membrane, when used as a supercapacitor electrode, can be modulated by the ionic charging state of the membrane, which gives rise to a collective electrolyte gating effect. This gating effect provides an in-operando approach for probing the charging dynamics of supercapacitors electrically. Using this approach, we observed a pore-size-dependent ionic hysteresis or memory effect in reduced graphene oxide membranes when the interlayer distance is comparable to the ion diameter. Our results may stimulate the design of novel devices based on the ion-electron interactions under nanoconfinement.

Beneficial restacking of 2D nanomaterials for electrocatalysis: a case of MoS2 membranes.

Restacking of 2D nanomaterials is often deemed to be detrimental to their applications. In contrast to this common notion, here we demonstrate that tightly packed stacked MoS2 exhibits a higher electrocatalytic activity for hydrogen evolution than the more loosely stacked ones.

Solvation-Involved Nanoionics: New Opportunities from 2D Nanomaterial Laminar Membranes.

Nanoporous laminar membranes composed of multilayered 2D nanomaterials (2D-NLMs) are increasingly being exploited as a unique material platform for understanding solvated ion transport under nanoconfinement and exploring novel nanoionics-related applications, such as ion sieving, energy storage and harvesting, and in other new ionic devices. Here, the fundamentals of solvation-involved nanoionics in terms of ionic interactions and their effect on ionic transport behaviors are discussed. This is followed by a summary of key requirements for materials that are being used for solvation-involved nanoionics research, culminating in a demonstration of unique features of 2D-NLMs. Selected examples of using 2D-NLMs to address the key scientific problems related to nanoconfined ion transport and storage are then presented to demonstrate their enormous potential and capabilities for nanoionics research and applications. To conclude, a personal perspective on the challenges and opportunities in this emerging field is presented.

Electrochemically-derived graphene oxide membranes with high stability and superior ionic sieving.

Crosslinker-free electrochemically-derived graphene oxide membranes are found to be extraordinarily stable in aqueous solutions and exhibit superior ionic sieving performance because of their unique chemical structure.

Polycrystalline Diamond Coating of Additively Manufactured Titanium for Biomedical Applications.

Additive manufacturing using selective laser melted titanium (SLM-Ti) is used to create bespoke items across many diverse fields such as medicine, defense, and aerospace. Despite great progress in orthopedic implant applications, such as for "just in time" implants, significant challenges remain with regards to material osseointegration and the susceptibility to bacterial colonization on the implant. Here, we show that polycrystalline diamond coatings on these titanium samples can enhance biological scaffold interaction improving medical implant applicability. The highly conformable coating exhibited excellent bonding to the substrate. Relative to uncoated SLM-Ti, the diamond coated samples showed enhanced mammalian cell growth, enriched apatite deposition, and reduced microbial S. aureus activity. These results open new opportunities for novel coatings on SLM-Ti devices in general and especially show promise for improved biomedical implants.

Molecular detection by liquid gated Hall effect measurements of graphene.

Conventional electrical biosensing techniques include Cyclic Voltammetry (CV, amperometric) and ion-sensitive field effect transistors (ISFETs, potentiometric). However, CV is not able to detect electrochemically inactive molecules where there is no redox reaction in solution, and the resistance change in pristine ISFETs in response to low concentration solutions is not observable. Here, we show a very sensitive label-free biosensing method using Hall effect measurements on unfunctionalized graphene devices where the gate electrode is immersed in the solution containing the analyte of interest. This liquid gated Hall effect measurement (LGHM) technique is independent of redox reactions, and it enables the extraction of additional information regarding electrical properties from graphene as compared with ISFETs, which can be used to improve the sensitivity. We demonstrate that LGHM has a higher sensitivity than conventional biosensing methods for l-histidine in the pM range. The detection mechanism is proposed to be based on the interaction between the ions and graphene. The ions could induce asymmetry in electron-hole mobility and inhomogeneity in graphene, and they may also respond to the Hall effect measurement. Moreover, the calculation of capacitance values shows that the electrical double layer capacitance is dominant at relatively high gate voltages in our system, and this is useful for applications including biosensing, energy storage, and neural stimulation.

Direct fabrication of 3D graphene on nanoporous anodic alumina by plasma-enhanced chemical vapor deposition.

High surface area electrode materials are of interest for a wide range of potential applications such as super-capacitors and electrochemical cells. This paper describes a fabrication method of three-dimensional (3D) graphene conformally coated on nanoporous insulating substrate with uniform nanopore size. 3D graphene films were formed by controlled graphitization of diamond-like amorphous carbon precursor films, deposited by plasma-enhanced chemical vapour deposition (PECVD). Plasma-assisted graphitization was found to produce better quality graphene than a simple thermal graphitization process. The resulting 3D graphene/amorphous carbon/alumina structure has a very high surface area, good electrical conductivity and exhibits excellent chemically stability, providing a good material platform for electrochemical applications. Consequently very large electrochemical capacitance values, as high as 2.1 mF for a sample of 10 mm(3), were achieved. The electrochemical capacitance of the material exhibits a dependence on bias voltage, a phenomenon observed by other groups when studying graphene quantum capacitance. The plasma-assisted graphitization, which dominates the graphitization process, is analyzed and discussed in detail.