Rational Design of Diamond Electrodes.

Diamond electrodes stepped onto the stage in the early 1990s for electroanalytical applications. They possess the features of long-term chemical inertness, wide potential windows, low and stable background currents, high microstructural stability at different potentials and in different media, varied activity toward different electroactive species, reliable electrochemical response of redox systems without conventional pretreatment, high resistance to surface fouling in most cases, and possibility of forming composites with different components such as other carbon materials, carbides, and oxidizes. Most diamond electrodes are prepared in microcrystalline or nanocrystalline form using chemical vapor deposition techniques. Starting from diamond films and diamond composites, numerous nanostructured diamond electrodes have also been produced. The features of diamond electrodes are therefore heavily dependent on the growth conditions and post-treatment procures that are applied on diamond electrodes such as introduced dopant(s), surface termination(s), surface functional group(s), added components, and final structure(s). Numerous applications of diamond electrodes have been explored in the fields of electrochemical sensing, electrosynthesis, electrocatalysis, electrochemical energy storage and conversion, devices, and environmental degradation.This Account summarizes our strategies to design different diamond electrodes, including diamond films, diamond composites, as well as their nanostructures. With respect to diamond films, the modulation of their dopant(s) and surface termination(s) as well as the attachment of functional modifier(s) onto their surface are discussed. Electrochemical hydrogenation and oxygenation of diamond electrodes are detailed at an atomic scale. As the examples of designing diamond electrodes at a molecular scale, photochemical and electrochemical attachment of modifier(s) onto diamond electrodes are shown. Moreover, electrochemical grafting of diazonium salts is proposed as a new technique to identify hydrogenated, hydroxylated, and oxygenated terminations of diamond electrodes. The introduction of additional component(s) into a diamond film to form diamond composites is then overviewed, where a hydrogen-induced selective growth model is proposed to elucidate the preparation of diamond/ß-SiC composites. Subsequently, the production of various diamond nanostructures from diamond films and composites by means of top-down, bottom-up, and template-free approaches is shown. Electrochemical application examples of diamond electrodes are overviewed, covering direct electrochemistry of natural Cytochrome c on a hydroxylated diamond surface, sensitive electrochemical DNA biosensing on tip-functionalized diamond nanowires, and construction of high-performance supercapacitors using diamond electrodes and redox electrolytes. Our diamond supercapacitors, also named battery-like diamond supercapacitors or diamond supercabatteries, are highlighted since they combine the features of supercapacitors and batteries. Future perspectives of diamond electrodes are outlined, ranging from their rational design and synthesis to their electrochemical applications in different fields.

Regulating d-Band Center of Ti2 C MXene Via Nb Alloying for Stable and High-Efficient Supercapacitive Performances.

Ti2 C MXene with the lowest formula weight is expected to gain superior advantages in gravimetric capacitances over other heavier MXenes. Nevertheless, its poor chemical and electrochemical stability is the most fatal drawback and seriously hinders its practical applications. Herein, an alloy engineering strategy at the transition metal-sites of Ti2 C MXene is proposed. Theoretical calculations reveal that the electronic redistribution of the solid-solution TiNbC MXene improves the electronic conductivity, induces the upward d-band center, tailors the surface functional groups, and increases the electron loss impedance, resulting in its excellent capacitive performance and high chemical stability. The as-prepared flexible TiNbC film delivers specific capacitance up to 381 F g-1 at a scan rate of 2 mV s-1 and excellent electrochemical stability without capacitance loss after 10000 charge/discharging cycles. This work provides a universal approach to develop high-performance and chemically stable MXene electrodes.

Metal Centers and Organic Ligands Determine Electrochemistry of Metal-Organic Frameworks.

The properties and applications of metal-organic frameworks (MOFs) can be tuned by their metal centers and organic ligands. To reveal experimentally and theoretically the influence of metal centers and ligands on electrochemical performance of MOFs, three MOFs with copper or zinc centers and organic ligands of 2-methylimidazole (2MI) or 1,3,5-benzenetricarboxylic acid (H3 BTC) are synthesized and characterized in this study. 2D and porous Cu-2MI exhibits a larger active area, faster electron transfer capability, and stronger adsorption capacity than bulk Cu-BTC and dodecahedron Zn-2MI. Density functional theory calculations of adsorption ability of three MOFs toward xanthine (XA), hypoxanthine (HXA), and malachite green (MG) prove that 2D Cu-2MI has the strongest adsorption energies to three targets. Rotating disk electrode measurements reveal that 2D Cu-2MI features the biggest intrinsic heterogeneous rate constant toward three analytes. On 2D Cu-2MI sensitive and selective monitoring of XA, HXA, and MG is then achieved using differential pulse voltammetry. Their monitoring in real samples on 2D Cu-2MI is accurate and comparable with that using high-performance liquid chromatography. In summary, regulation of electrochemical sensing features of MOFs is realized through defining selected metal centers and organic ligands.

Graphdiyne Electrochemistry: Progress and Perspectives.

Graphdiyne, a carbon allotrope, was synthesized in 2010 for the first time. It consists of two acetylene bonds between adjacent benzene rings. Graphdiyne and its composites thus exhibit ultrahigh intrinsic electrochemical activities. As "star" electrode materials, they have been utilized for various electrochemical applications. With the aim of giving a full screen of graphdiyne electrochemistry, this review starts from the history of graphdiyne materials, followed by their structural and electrochemical features. Recent progress and achievements in the synthesis of graphdiyne materials and their composites are overviewed. Subsequently, various electrochemical applications of graphdiyne materials and their composites are summarized, covering those in the fields of electrochemical energy conversion, electrochemical energy storage, and electrochemical sensing. The perspectives of graphdiyne electrochemistry are also discussed and outlined.

Coupling W18 O49 /Ti3 C2 Tx MXene Pseudocapacitive Electrodes with Redox Electrolytes to Construct High-Performance Asymmetric Supercapacitors.

A pseudocapacitive electrode with a large surface area is critical for the construction of a high-performance supercapacitor. A 3D and interconnected network composed of W18 O49 nanoflowers and Ti3 C2 Tx MXene nanosheets is thus synthesized using an electrostatic attraction strategy. This composite effectively prevents the restacking of Ti3 C2 Tx MXene nanosheets and meanwhile sufficiently exposes electrochemically active sites of W18 O49 nanoflowers. Namely, this self-assembled composite owns abundant oxygen vacancies from W18 O49 nanoflowers and enough active sites from Ti3 C2 Tx MXene nanosheets. As a pseudocapacitive electrode, it shows a big specific capacitance, superior rate capability and good cycle stability. A quasi-solid-state asymmetric supercapacitor (ASC) is then fabricated using this pseudocapacitive anode and the cathode of activated carbon coupled with a redox electrolyte of FeBr3 . This ASC displays a cell voltage of 1.8 V, a capacitance of 101 F g-1 at a current density of 1 A g-1 , a maximum energy density of 45.4 Wh kg-1 at a power density of 900 W kg-1 , and a maximum power density of 18 000 W kg-1 at an energy density of 10.8 Wh kg-1 . The proposed strategies are promising to synthesize different pseudocapacitive electrodes as well as to fabricate high-performance supercapacitor devices.

Freeze-Tolerant Hydrogel Electrolyte with High Strength for Stable Operation of Flexible Zinc-Ion Hybrid Supercapacitors.

Constructing ionic conductive hydrogels with diversified properties is crucial for portable zinc-ion hybrid supercapacitors (ZHSCs). Herein, a freeze-tolerant hydrogel electrolyte (AF PVA-CMC/Zn(CF3 SO3 )2 ) is developed by forming a semi-interpenetrating anti-freezing polyvinyl alcohol-carboxymethyl cellulose (AF PVA-CMC) network filled with the ethylene glycol (EG)-containing Zn(CF3 SO3 )2 aqueous solution. The semi-interpenetrating AF PVA-CMC/Zn(CF3 SO3 )2 possesses enhanced mechanical properties, realizes the uniform zinc deposition, and impedes the dendrite growth. Notably, the interaction between PVA and EG suppresses the ice crystal formation and prevents freezing at -20 °C. Due to these advantages, the designed hydrogel owns high ionic conductivity of 1.73/0.75 S m-1 at 20/-20 °C with excellent tensile/compression strength at 20 °C. Impressively, the flexible AF quasi-solid-state ZHSC employing the hydrogel electrolyte achieves a superior energy density at 20/-20 °C (87.9/60.7 Wh kg-1 ). It maintains nearly 84.8% of the initial capacity after 10 000 cycles and a low self-discharge rate (1.77 mV h-1 ) at 20 °C, together with great tolerance to corrosion. Moreover, this device demonstrates a stable electrochemical performance at -20 °C under deformation. The obtained results provide valuable insights for constructing durable hydrogel electrolytes in cold environments.

Design and Fabrication of Hierarchical NiCoP-MOF Heterostructure with Enhanced Pseudocapacitive Properties.

Metal-organic framework (MOF)-derived heterostructures possessing the merits of each component are thought to display the enhanced energy storage performance due to their synergistic effect. Herein, a functional heterostructure (NiCoP-MOF) composed of nickel/cobalt-MOF (NiCo-MOF) and phosphide (NiCoP) is designed and fabricated via the localized phosphorization of unusual lamellar brick-stacked NiCo-MOF assemblies obtained by a hydrothermal method. The experimental and computational analyses reveal that such-fabricated heterostructures possess the modulated electronic structure, abundant active sites, and hybrid crystalline feature, which is kinetically beneficial for fast electron/ion transport to enhance the charge storage capability. Examined as the supercapacitor electrode, the obtained NiCoP-MOF compared to the NiCo-MOF delivers a high capacity of 728 C g-1 (1.82 C cm-2 ) at 1 A g-1 with a high capacity retention of 430 C g-1 (1.08 C cm-2 ) when increasing the current density to 20 A g-1 . Importantly, the assembled solid-state NiCoP-MOF-based hybrid supercapacitor displays superior properties regarding the capacity (226.3 C g-1 ), energy density (50.3 Wh kg-1 ), and durability (≈100% capacity retention over 10 000 cycles). This in situ heterogenization approach sheds light on the electronic structure modulation while maintaining the well-defined porosity and morphology, holding promise for designing MOF-based derivatives for high performance energy storage devices.

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.

A Phosphorus-Doped Ag@Pd Catalyst for Enhanced CC Bond Cleavage during Ethanol Electrooxidation.

Ethanol is preferred to be oxidized into CO2 for the construction of a high-performance direct ethanol fuel cell since this complete ethanol oxidation reaction (EOR) transfers 12 electrons. However, this EOR is sluggish and has the low activity as well as poor selectivity. To promote such a favorable EOR, more exactly the cleavage selectivity of CC bonds in ethanol, phosphorus-doped silver-core-and-Pd-shell catalysts (denoted as Ag@PdP) are designed and synthesized. In the alkaline media, a Ag@Pd2 P0.2 catalyst is superior toward EOR into CO2 . It exhibits seven times higher mass activity and six times higher selectivity than the benchmark Pd/C catalyst. As confirmed by means of density functional theory calculation and in situ Fourier-transform infrared spectroscopy, such high performance stems from an increased adsorption energy of OH radicals on the Pd active sites. Meanwhile, the tensile strain effect of a core-shell structure of this Ag@Pd2 P0.2 catalyst favors the formation of adsorbed CH3 CO intermediate, the key species for the enhanced C-C cleavage into CO2 , instead of acetate. The proposed way to design and synthesize such high-performance EOR catalysts will explore the practical applications of direct alkaline ethanol fuel cells.

Epitaxial Cubic Silicon Carbide Photocathodes for Visible-Light-Driven Water Splitting.

Cubic silicon carbide (3C-SiC) material feature a suitable bandgap and high resistance to photocorrosion. Thus, it has been emerged as a promising semiconductor for hydrogen evolution. Here, the relationship between the photoelectrochemical properties and the microstructures of different SiC materials is demonstrated. For visible-light-derived water splitting to hydrogen production, nanocrystalline, microcrystalline and epitaxial (001) 3C-SiC films are applied as the photocathodes. The epitaxial 3C-SiC film presents the highest photoelectrochemical activity for hydrogen evolution, because of its perfect (001) orientation, high phase purity, low resistance, and negative conduction band energy level. This finding offers a strategy to design SiC-based photocathodes with superior photoelectrochemical performances.

Tailoring the CeO2 morphology and its electrochemical reactivity for highly sensitive and selective determination of dopamine and epinephrine.

Four CeO2 nanomaterials with the morphologies of a nanoplate (CeO2-p), a nanocube (CeO2-c), a porous triangular microplate (CeO2-t), and of a porous hierarchical rod-stacked nanobundle (CeO2-b) were synthesized using a hydrothermal method. They were characterized by scanning and transmission electron microscopies, X-ray diffraction and X-ray photoelectron spectroscopy. Electrochemical characterizations reveal the tuning of their morphology and the presence of exposed crystal planes of CeO2 that can be realized by changing the alkali sources. Among these materials, the CeO2-b features the largest specific surface and lowest electron transfer resistance towards the redox probe Fe(CN)63-/4-. The best voltammetric response to dopamine and epinephrine is thus achieved by using the Nafion-CeO2-b coated electrode. A sensitive and selective method was developed that can voltammetrically detect dopamine (with a peak near 0.13 V vs. SCE), and epinephrine (with a peak near 0.25 V vs. SCE). The detection limits are 2.9 and 0.67 nM, respectively. Graphical abstractSchematic representation of morphology tailoring of CeO2 and electrochemical sensing of dopamine and epinephrine on these CeO2 samples with different morphologies.

Conductive diamond: synthesis, properties, and electrochemical applications.

Conductive diamond possesses unique features as compared to other solid electrodes, such as a wide electrochemical potential window, a low and stable background current, relatively rapid rates of electron-transfer for soluble redox systems without conventional pretreatment, long-term responses, stability, biocompatibility, and a rich surface chemistry. Conductive diamond microcrystalline and nanocrystalline films, structures and particles have been prepared using a variety of approaches. Given these highly desirable attributes, conductive diamond has found extensive use as an enabling electrode across a variety of fields encompassing chemical and biochemical sensing, environmental degradation, electrosynthesis, electrocatalysis, and energy storage and conversion. This review provides an overview of the fundamental properties and highlights recent progress and achievements in the growth of boron-doped (metal-like) and nitrogen and phosphorus-doped (semi-conducting) diamond and hydrogen-terminated undoped diamond electrodes. Applications in electroanalysis, environmental degradation, electrosynthesis electrocatalysis, and electrochemical energy storage are also discussed. Diamond electrochemical devices utilizing micro-scale, ultramicro-scale, and nano-scale electrodes as well as their counterpart arrays are viewed. The challenges and future research directions of conductive diamond are discussed and outlined. This review will be important and informative for chemists, biochemists, physicists, materials scientists, and engineers engaged in the use of these novel forms of carbon.

Recent Advances of Porous Graphene: Synthesis, Functionalization, and Electrochemical Applications.

Graphene is a 2D sheet of sp2 bonded carbon atoms and tends to aggregate together, due to the strong π-π stacking and van der Waals attraction between different layers. Its unique properties such as a high specific surface area and a fast mass transport rate are severely blocked. To address these issues, various kinds of 2D holey graphene and 3D porous graphene are either self-assembled from graphene layers or fabricated using graphene related materials such as graphene oxide and reduced graphene oxide. Porous graphene not only possesses unique pore structures, but also introduces abundant exposed edges and accelerates mass transfer. The properties and applications of these porous graphenes and their composites/hybrids have been extensively studied in recent years. Herein, recent progress and achievements in synthesis and functionalization of various 2D holey graphene and 3D porous graphene are reviewed. Of special interest, electrochemical applications of porous graphene and its hybrids in the fields of electrochemical sensing, electrocatalysis, and electrochemical energy storage, are highlighted. As the closing remarks, the challenges and opportunities for the future research of porous graphene and its composites are discussed and outlined.

Atomic Carbon Layers Supported Pt Nanoparticles for Minimized CO Poisoning and Maximized Methanol Oxidation.

Maximizing activity of Pt catalysts toward methanol oxidation reaction (MOR) together with minimized poisoning of adsorbed CO during MOR still remains a big challenge. In the present work, uniform and well-distributed Pt nanoparticles (NPs) grown on an atomic carbon layer, that is in situ formed by means of dry-etching of silicon carbide nanoparticles (SiC NPs) with CCl4 gas, are explored as potential catalysts for MOR. Significantly, as-synthesized catalysts exhibit remarkably higher MOR catalytic activity (e.g., 647.63 mA mg-1 at a peak potential of 0.85 V vs RHE) and much improved anti-CO poisoning ability than the commercial Pt/C catalysts, Pt/carbon nanotubes, and Pt/graphene catalysts. Moreover, the amount of expensive Pt is a few times lower than that of the commercial and reported catalyst systems. As confirmed from density functional theory (DFT) calculations and X-ray absorption fine structure (XAFS) measurements, such high performance is due to reduced adsorption energy of CO on the Pt NPs and an increased amount of adsorbed energy OH species that remove adsorbed CO fast and efficiently. Therefore, these catalysts can be utilized for the development of large-scale and industry-orientated direct methanol fuel cells.

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.

ZnS/C/MoS2 Nanocomposite Derived from Metal-Organic Framework for High-Performance Photo-Electrochemical Immunosensing of Carcinoembryonic Antigen.

A hexafluorophosphate ionic liquid is used as a functional monomer to prepare a metal-organic framework (Zn-MOF). Zn-MOF is used as a template for MoS2 nanosheets synthesis and further carbonized to yield light-responsive ZnS/C/MoS2 nanocomposites. Zn-MOF, carbonized-Zn-MOF, and ZnS/C/MoS2 nanocomposites are characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, X-ray diffraction pattern, scanning electron microscopy (SEM), element mapping, Raman spectroscopy, X-ray photoelectron spectroscopy, fluorescence, and nitrogen-adsorption analysis. Carcinoembryonic antigen (CEA) is selected as a model to construct an immunosensing platform to evaluate the photo-electrochemical (PEC) performances of ZnS/C/MoS2 nanocomposites. A sandwich-type PEC immunosensor is fabricated by immobilizing CEA antibody (Ab1 ) onto the ZnS/C/MoS2 /GCE surface, subsequently binding CEA and the alkaline phosphatase-gold nanoparticle labeled CEA antibody (ALP-Au-Ab2 ). The catalytic conversion of vitamin C magnesium phosphate produces ascorbic acid (AA). Upon being illuminated, AA can react with photogenerated holes from ZnS/C/MoS2 nanocomposites to generate a photocurrent for quantitative assay. Under optimized experimental conditions, the PEC immunosensor exhibits excellent analytical characteristics with a linear range from 2.0 pg mL-1 to 10.0 ng mL-1 and a detection limit of 1.30 pg mL-1 (S/N = 3). The outstanding practicability of this PEC immunosensor is demonstrated by accurate assaying of CEA in clinical serum samples.

3D 3C-SiC/Graphene Hybrid Nanolaminate Films for High-Performance Supercapacitors.

High-performance supercapacitors feature big and stable capacitances and high power and energy densities. To fabricate high-performance supercapacitors, 3D 3C-SiC/graphene hybrid nanolaminate films are grown via a microwave plasma-assisted chemical vapor deposition technique. Such films consist of 3D alternating structures of vertically aligned 3C-SiC and graphene layers, leading to high surface areas and excellent conductivity. They are further applied as the capacitor electrodes to construct electrical double layer capacitors (EDLCs) and pseudocapacitors (PCs) in both aqueous and organic solutions. The capacitance for an EDLC in aqueous solutions is up to 549.9 µF cm-2 , more than 100 times higher than that of an epitaxial 3C-SiC film. In organic solutions, it is 297.3 µF cm-2 . The pseudocapacitance in redox-active species (0.05 Fe(CN)6 3-/4- ) contained aqueous solutions is as high as 62.2 mF cm-2 . The capacitance remains at 98% of the initial value after 2500 charging/discharging cycles, indicating excellent cyclic stability. In redox-active species (0.01 m ferrocene) contained organic solutions, it is 16.6 mF cm-2 . Energy and power densities of a PC in aqueous solution are 11.6 W h kg-1 and 5.1 kW kg-1 , respectively. These vertically aligned 3C-SiC/graphene hybrid nanolaminate films are thus promising electrode materials for energy storage applications.

Shape-Controlled Growth of Carbon Nanostructures: Yield and Mechanism.

Carbon nanostructures with precisely controlled shapes are difficult materials to synthesize. A facet-selective-catalytic process was thus proposed to synthesize polymer-linked carbon nanostructures with different shapes, covering straight carbon nanofiber, carbon nano Y-junction, carbon nano-hexapus, and carbon nano-octopus. A thermal chemical vapor deposition process was applied to grow these multi-branched carbon nanostructures at temperatures lower than 350 °C. Cu nanoparticles were utilized as the catalyst and acetylene as the reaction gas. The growth of those multi-branched nanostructures was realized through the selective growth of polymer-like sheets on certain indexed facets of Cu catalyst. The vapor-facet-solid (VFS) mechanism, a new growth mode, has been proposed to interpret such a growth in the steps of formation, diffusion, and coupling of carbon-containing oligomers, as well as their final precipitation to form nanostructures on the selective Cu facets.