Enhancing Interfacial Capacitance by Boron Doping in Vertically Porous Carbon Toward High-Performance AC Filtering Electrochemical Capacitors.

Electrochemical capacitors (ECs) show great perspective in alternate current (AC) filtering once they simultaneously reach ultra-fast response and high capacitance density. Nevertheless, the structure-design criteria of the two key properties are often mutually incompatible in electrode construction. Herein, it is proposed that combining vertically oriented porous carbon with enhanced interfacial capacitance (Ci) can efficiently solve this issue. Theoretically, the density function theory calculation shows that the Ci of a carbon electrode can be enhanced by boron doping due to the corresponding compact induced charge layer. Experimentally, the vertical-oriented boron-doped graphene nanowalls (BGNWs) electrodes, whose Ci is enhanced from 4.20 to 10.16 µF cm-2 upon boron doping, are prepared on a large scale (480 cm2) using a hot-filament chemical vapor deposition technique (HFCVD). Owing to the high Ci and vertically oriented porous structure, BGNWs-based EC has a high capacitance density of 996 µF cm-2 with a phase angle of - 79.4° at 120 Hz in aqueous electrolyte and a high energy density of 1953 µFV2 cm-2 in organic electrolyte. As a result, the EC is capable of smoothing 120 Hz ripples for 60 Hz AC filtering. These results provide enlightening insights on designing high-performance ECs for high-frequency applications.

Nitrogen-doped carbon nanowalls/diamond films as efficient electrocatalysts toward oxygen reduction reaction.

Substitution of commercial Pt/C electrocatalysts with efficient carbon-based ones for oxygen reduction reaction (ORR) still remains a huge challenge. For practical ORR applications it is significant to design robust 3D network nanostructures in that they do not require polymer binders. For conventional powder catalysts, they must be combined with substrate, leading to their shedding and degradation. In this work, vertically-aligned N-doped carbon nanowalls/diamond (N-CNWs/D) films are synthesized by means of a microwave plasma chemical vapor deposition technique, where nitrogen doping is conducted during the growth process and a subsequent facile annealing treatment under Ar atmosphere. The obtained Ar treated N-CNWs/D film exhibits an ORR onset potential of 835 mV (versus reversible hydrogen electrode) in 0.1 mol l-1KOH solution in a four-electron reaction pathway. It also displays excellent tolerance toward methanol crossover and long-term stability (e.g. a current density loss of only 10% even after 16 h measurement). The boosting ORR performance can be attributed to the activated pyridinic N dopant at abundant edge sites and enlarged electrochemical surface areas of N-CNWs/D films. This work not only develops a controllable strategy to fabricate binder-free carbon-based ORR electrocatalysts, but also paves a way to in-depth understand actual active sites in terms of ORR pathway mechanisms.

Rational Construction of 3D-Networked Carbon Nanowalls/Diamond Supporting CuO Architecture for High-Performance Electrochemical Biosensors.

Tremendous demands for highly sensitive and selective nonenzymatic electrochemical biosensors have motivated intensive research on advanced electrode materials with high electrocatalytic activity. Herein, the 3D-networked CuO@carbon nanowalls/diamond (C/D) architecture is rationally designed, and it demonstrates wide linear range (0.5 × 10-6 -4 × 10-3 m), high sensitivity (1650 µA cm-2 mm-1 ), and low detection limit (0.5 × 10-6 m), together with high selectivity, great long-term stability, and good reproducibility in glucose determination. The outstanding performance of the CuO@C/D electrode can be ascribed to the synergistic effect coming from high-electrocatalytic-activity CuO nanoparticles and 3D-networked conductive C/D film. The C/D film is composed of carbon nanowalls and diamond nanoplatelets; and owing to the large surface area, accessible open surfaces, and high electrical conduction, it works as an excellent transducer, greatly accelerating the mass- and charge-transport kinetics of electrocatalytic reaction on the CuO biorecognition element. Besides, the vertical aligned diamond nanoplatelet scaffolds could improve structural and mechanical stability of the designed electrode in long-term performance. The excellent CuO@C/D electrode promises potential application in practical glucose detection, and the strategy proposed here can also be extended to construct other biorecognition elements on the 3D-networked conductive C/D transducer for various high-performance nonenzymatic electrochemical biosensors.

Photochemical Modification of Single Crystalline GaN Film Using n-Alkene with Different Carbon Chain Lengths as Biolinker.

As a potential material for biosensing applications, gallium nitride (GaN) films have attracted remarkable attention. In order to construct GaN biosensors, a corresponding immobilization of biolinkers is of great importance in order to render a surface bioactive. In this work, two kinds of n-alkenes with different carbon chain lengths, namely allylamine protected with trifluoroacetamide (TFAAA) and 10-aminodec-1-ene protected with trifluoroacetamide (TFAAD), were used to photochemically functionalize single crystalline GaN films. The successful linkage of both TFAAA and TFAAD to the GaN films is confirmed by time-of-flight secondary ion mass spectrometry (ToF-SIMS) measurement. With increased UV illumination time, the intensity of the secondary ions corresponding to the linker molecules initially increases and subsequently decreases in both cases. Based on the SIMS measurements, the maximum coverage of TFAAA is achieved after 14 h of UV illumination, while only 2 h is required in the case of TFAAD to reach the situation of a fully covered GaN surface. This finding leads to the conclusion that the reaction rate of TFAAD is significantly higher compared to TFAAA. Measurements by atomic force microscopy (AFM) indicate that the coverage of GaN films by a TFAAA layer leads to an increased surface roughness. The atomic terraces, which are clearly observable for the pristine GaN films, disappear once the surface is fully covered by a TFAAA layer. Such TFAAA layers will feature a homogeneous surface topography even for reaction times of 24 h. In contrast to this, TFAAD shows strong cross-polymerization on the surface, this is confirmed by optical microscopy. These results demonstrate that TFAAA is a more suitable candidate as biolinker in context of the GaN surfaces due to its improved controllability.

Fluorine-Modulated MXene-Derived Catalysts for Multiphase Sulfur Conversion in Lithium-Sulfur Battery.

Fluorine owing to its inherently high electronegativity exhibits charge delocalization and ion dissociation capabilities; as a result, there has been an influx of research studies focused on the utilization of fluorides to optimize solid electrolyte interfaces and provide dynamic protection of electrodes to regulate the reaction and function performance of batteries. Nonetheless, the shuttle effect and the sluggish redox reaction kinetics emphasize the potential bottlenecks of lithium-sulfur batteries. Whether fluorine modulation regulate the reaction process of Li-S chemistry? Here, the TiOF/Ti3C2 MXene nanoribbons with a tailored F distribution were constructed via an NH4F fluorinated method. Relying on in situ characterizations and electrochemical analysis, the F activates the catalysis function of Ti metal atoms in the consecutive redox reaction. The positive charge of Ti metal sites is increased due to the formation of O-Ti-F bonds based on the Lewis acid-base mechanism, which contributes to the adsorption of polysulfides, provides more nucleation sites and promotes the cleavage of S-S bonds. This facilitates the deposition of Li2S at lower overpotentials. Additionally, fluorine has the capacity to capture electrons originating from Li2S dissolution due to charge compensation mechanisms. The fluorine modulation strategy holds the promise of guiding the construction of fluorine-based catalysts and facilitating the seamless integration of multiple consecutive heterogeneous catalytic processes.

A Highly Active Porous Mo2C-Mo2N Heterostructure on Carbon Nanowalls/Diamond for a High-Current Hydrogen Evolution Reaction.

Developing non-precious metal-based electrocatalysts operating in high-current densities is highly demanded for the industry-level electrochemical hydrogen evolution reaction (HER). Here, we report the facile preparation of binder-free Mo2C-Mo2N heterostructures on carbon nanowalls/diamond (CNWs/D) via ultrasonic soaking followed by an annealing treatment. The experimental investigations and density functional theory calculations reveal the downshift of the d-band center caused by the heterojunction between Mo2C/Mo2N triggering highly active interfacial sites with a nearly zero ∆GH* value. Furthermore, the 3D-networked CNWs/D, as the current collector, features high electrical conductivity and large surface area, greatly boosting the electron transfer rate of HER occurring on the interfacial sites of Mo2C-Mo2N. Consequently, the self-supporting Mo2C-Mo2N@CNWs/D exhibits significantly low overpotentials of 137.8 and 194.4 mV at high current densities of 500 and 1000 mA/cm2, respectively, in an alkaline solution, which far surpass the benchmark Pt/C (228.5 and 359.3 mV) and are superior to most transition-metal-based materials. This work presents a cost-effective and high-efficiency non-precious metal-based electrocatalyst candidate for the electrochemical hydrogen production industry.

In Situ Construction of Hierarchical Diamond Supported on Carbon Nanowalls/Diamond for Enhanced Electron Field Emission.

The integration of sp2-/sp3-bonded carbon has aroused increasing attention on attaining a great electron field emission (EFE) performance. Herein, a novel hierarchical diamond@carbon nanowalls/diamond (D@C/D) architecture is facilely prepared through the growth of the hybrid carbon nanowalls/diamond (C/D) film followed by the in situ hydrogen plasma treatment using microwave plasma chemical vapor deposition. The hierarchical D@C/D architecture is composed of thin diamond nanoplatelets sandwiched into carbon nanowalls (CNWs) as the bottom layer and the thickened nanoplatelets constituted by diamond nanograins as the upper layer. The hydrogen plasma plays an effective role in the transformation of sacrificial sp2-bonded CNWs to sp3-bonded diamond, eventually leading to the template thickening of diamond nanoplatelets in the upper layer. Impressively, the D@C/D-90 film demonstrates much better EFE behaviors of low turn-on potential (Eo = 4.3 V µm-1), high current density (Je@8 V µm-1 = 20.81 mA cm-1), and superior long-term stability, in comparison with the pristine C/D film (Eo = 6 V µm-1, Je@8 V µm-1 = 0.33 mA cm-1). The enhanced EFE performance of the hierarchical D@C/D film is ascribed to the well-established graphite pathway for electrons transported from the bottom to the top and the increased diamond emitting sites with negative electron-affinity and robust nature at the top. This work will promote the development of the high-performance cathode EFE material based on hybrid sp2/sp3-bonded carbon, and the method proposed here also provides an effective strategy to construct a diamond nanostructure for various applications.

Antibacterial durability and biocompatibility of antibacterial-passivated 316L stainless steel in simulated physiological environment.

Stainless steel (SS) has been widely applied as one of the most efficient implant metal materials, although corrosion and infection in body environment are still challenging. Herein, an antibacterial passivation method was employed to enhance the antibacterial performance and corrosion resistance of the medical 316L SS. The result proved that the antibacterial-passivated 316L SS exhibited stable antibacterial activity and effectively inhibited the formation of bacterial biofilm. Electrochemical measurements combined with X-ray photoelectron spectroscopy technique were used to study the corrosion resistance and semiconductor behavior of passivated 316L SS immersed in simulated physiological environment. The results indicated that the 316L SS after antibacterial passivation treatment for 1 h, soaking in the medium for 10 days, showed satisfactory corrosion resistance attributing to proper Cu deposition in the passive film. The anodic stripping voltammetry measurement further confirmed that the Cu-bearing passive film could continuously release Cu ions into medium. The zebrafish test demonstrated an excellent in vivo biocompatibility for the 316L SS with antibacterial passivation for 0.5 and 1 h, respectively. In addition, changes of surface roughness, contact angle and chemical composition after antibacterial passivation played an important role in explaining the antibacterial mechanism, which could be clearly divided into contact killing and ionic release killing. Hence, the antibacterial passivation treatment was preliminarily proved as a potential way for enhancing the persistent antibacterial activity and corrosion resistance of 316L SS.

Hydration-induced nano- to micro-scale self-recovery of the tooth enamel of the giant panda.

The tooth enamel of vertebrates comprises a hyper-mineralized bioceramic, but is distinguished by an exceptional durability to resist impact and wear throughout the lifetime of organisms; however, enamels exhibit a low resistance to the initiation of large-scale cracks comparable to that of geological minerals based on fracture mechanics. Here we reveal that the tooth enamel, specifically from the giant panda, is capable of developing durability through counteracting the early stage of damage by partially recovering its innate geometry and structure at nano- to micro- length-scales autonomously. Such an attribute results essentially from the unique architecture of tooth enamel, specifically the vertical alignment of nano-scale mineral fibers and micro-scale prisms within a water-responsive organic-rich matrix, and can lead to a decrease in the dimension of indent damage in enamel introduced by indentation. Hydration plays an effective role in promoting the recovery process and improving the indentation fracture toughness of enamel (by ∼73%), at a minor cost of micro-hardness (by ∼5%), as compared to the dehydrated state. The nano-scale mechanisms that are responsible for the recovery deformation, specifically the reorientation and rearrangement of mineral fragments and the inter- and intra-prismatic sliding between constituents that are closely related to the viscoelasticity of organic matrix, are examined and analyzed with respect to the structure of tooth enamel. Our study sheds new light on the strategies underlying Nature's design of durable ceramics which could be translated into man-made systems in developing high-performance ceramic materials. STATEMENT OF SIGNIFICANCE: Tooth enamel plays a critical role in the function of teeth by providing a hard surface layer to resist wear/impact throughout the lifetime of organisms; however, such enamel exhibits a remarkably low resistance to the initiation of large-scale cracks, of hundreds of micrometers or more, comparable to that of geological minerals. Here we reveal that tooth enamel, specifically that of the giant panda, is capable of partially recovering its geometry and structure to counteract the early stages of damage at nano- to micro-scale dimensions autonomously. Such an attribute results essentially from the architecture of enamel but is markedly enhanced by hydration. Our work discerns a series of mechanisms that lead to the deformation and recovery of enamel and identifies a unique source of durability in the enamel to accomplish this function. The ingenious design of tooth enamel may inspire the development of new durable ceramic materials in man-made systems.