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Integrating carbon nitride with graphene into a lateral heterojunction would avoid energy loss within the interlaminar space region on conventional composites. To date, its synthesis process is limited to the bottom-up method which lacks the targeting and homogeneity. Herein, we proposed a hydrogen-initiated chemical epitaxial growth strategy at a relatively low temperature for the fabrication of graphene/carbon nitride in-plane heterostructure. Theoretical and experimental analysis proved that methane via in situ generation from the hydrogenated decomposition of carbon nitride triggered the graphene growth along the active sites at the edges of confined spaces. With the enhanced electrical field from the deposited graphene (0.5%), the performances on selective photo-oxidation and photocatalytic water splitting were promoted by 5.5 and 3.7 times, respectively. Meanwhile, a 7720 μmol/h/g(graphene) hydrogen evolution rate was acquired without any cocatalysts. This study provides an top-down strategy to synthesize in-plane catalyst for the utilization of solar energy.

Supported single atom catalysts (SACs), emerging as a new class of catalytic materials, have been attracting increasing interests. Here we developed a Ni SAC on microwave exfoliated graphene oxide (Ni-N-MEGO) to achieve single atom loading of ∼6.9 wt%, significantly higher than previously reported SACs. The atomically dispersed Ni atoms, stabilized by coordination with nitrogen, were found to be predominantly anchored along the edges of nanopores (

Ce/Ti mixed metal oxide thin films have well known optoelectrical properties amongst several other physio-chemical properties. Changes in the structural and mechanical properties of magnetron sputtered Ce/Ti oxide thin films on Si (100) wafers with different Ce:Ti ratios are investigated experimentally and by modelling. X-ray Photoemission Spectroscopy (XPS) and X-ray diffraction (XRD) confirm the primary phases as trigonal Ce2O3 and rutile form of TiO2 with SiO2 present in all prepared materials. FESEM imaging delivers information based on the variation of grain size, the mixed Ce/Ti oxides providing much smaller grain sizes in the thin film/substrate composite. Nanoindentation analysis concludes that the pure cerium oxide film has the highest hardness value (20.1 GPa), while the addition of excess titanium oxide decreases the hardness of the film coatings. High temperature in-situ XRD (up to 1000 degrees C) results indicate high thermal phase stability for all materials studied. The film with Ce:Ti = 68%:32% has a new additional minor oxide phase above 800 degrees C. Contact angle experiments suggest that the chemical composition of the surface is insignificant affecting the water contact angle. Results show a narrow band of 87.7-95.7 degrees contact angle. The finite element modelling (FEM) modelling of Ce/Ti thin film coatings based on Si(100); Si(110); silica and steel substrates shows a variation in stress concentration.

Metal oxides have been extensively applied as heterogeneous catalysts in various chemical processes, including conventional heterogeneous catalysis, photocatalysis, and membrane catalysis. The catalytic performance of an oxide heterogeneous catalyst can be affected by its lattice structure, electronic structure, surface properties, bulk defects, and metal–oxygen bond strength. As a catalytic membrane, the catalytic performance of an oxide may also strongly depend on its oxygen-ion diffusion properties. Cation doping has been extensively adopted to tailor, both physically and chemically, the properties of oxide materials, such as lattice structure, electronic structure, lattice defects and diffusion behavior, so as to alter their catalytic performance for various redox reactions. Very recently, anion doping into the oxygen site has emerged as a new strategy for tuning the chemical and physical properties of metal oxides, and thus for regulating their catalytic behavior. Here, a timely review of recent progress in the development of advanced oxide catalysts based on oxygen-site anion doping is provided. Emphasis is given to the effect of doping anions into the metal oxide lattice on the physical and chemical properties, and consequently the performance in various catalytic applications, including the oxidative dehydrogenation of ethane (ODE), oxidative coupling of methane (OCM), photocatalytic reduction of dyes, and ceramic membrane-based oxygen separation. The aim of the current review is to offer some insightful perspectives to guide the development of functional oxide materials based on the anion site doping strategy toward application in heterogeneous catalysis. The knowledge gained here may also be useful for other application fields, such as electrochemical energy storage devices and sensors.

The development of oxygen evolution reaction (OER) electrocatalysts remains a major challenge that requires significant advances in both mechanistic understanding and material design. Recent studies show that oxygen from the perovskite oxide lattice could participate in the OER via a lattice oxygen-mediated mechanism, providing possibilities for the development of alternative electrocatalysts that could overcome the scaling relations-induced limitations found in conventional catalysts utilizing the adsorbate evolution mechanism. Here we distinguish the extent to which the participation of lattice oxygen can contribute to the OER through the rational design of a model system of silicon-incorporated strontium cobaltite perovskite electrocatalysts with similar surface transition metal properties yet different oxygen diffusion rates. The as-derived silicon-incorporated perovskite exhibits a 12.8-fold increase in oxygen diffusivity, which matches well with the 10-fold improvement of intrinsic OER activity, suggesting that the observed activity increase is dominantly a result of the enhanced lattice oxygen participation., While water splitting provides a renewable means to store energy, the sluggish O2 evolution half-reaction limits applications. Here, authors examine a silicon-incorporated strontium cobaltite perovskite and correlate lattice oxygen participation in O2 evolution to the oxygen ion diffusivity.

Gold nanorods are one of the most widely explored inorganic materials in nanomedicine for diagnostics, therapeutics and sensing1. It has been shown that gold nanorods are not cytotoxic and localize within cytoplasmic vesicles following endocytosis, with no nuclear localization2,3, but other studies have reported alterations in gene expression profiles in cells following exposure to gold nanorods, via unknown mechanisms4. In this work we describe a pathway that can contribute to this phenomenon. By mapping the intracellular chemical speciation process of gold nanorods, we show that the commonly used Au–thiol conjugation, which is important for maintaining the noble (inert) properties of gold nanostructures, is altered following endocytosis, resulting in the formation of Au(i)–thiolates that localize in the nucleus5. Furthermore, we show that nuclear localization of the gold species perturbs the dynamic microenvironment within the nucleus and triggers alteration of gene expression in human cells. We demonstrate this using quantitative visualization of ubiquitous DNA G-quadruplex structures, which are sensitive to ionic imbalances, as an indicator of the formation of structural alterations in genomic DNA. The release of nuclear-localizing gold species from intracellular gold nanorods may alter gene expression on interaction with the genomic DNA.

Nanofibrous NiAl2O4/Al2O3 ceramic was prepared by electrospinning and subsequent calcination at 1000 °C. Under reducing atmosphere, Ni nanoparticles in situ grew from and were rooted in nanofibrous support. The anchored Ni-NiOx nanocatalysts showed the strong interaction with Al2O3-NiAl2O4 supports owing to the incompletion of NiAl2O4 and NiO reduction and therefore high resistances to aggregation and carbon formation. The nanofibrous catalysts have the advantages of both metal gauze catalysts (fast mass transfer) and supported catalysts (nanosized catalysts). Compared with conventional supported Ni-based catalysts, the nanofibours catalysts produced the highest syngas production during methane partial oxidation at the highest recorded gas hourly space velocity of 8 × 106 L∙Kg−1 h−1. The catalytic reaction was operated for 10 h without noticeable performance degradation and the fibrous structure of the nanocatalysts was retained.

Bismuth oxide is as an active promoter in enhancing the ionic conductivity and electrocatalytic activity of manganite oxygen electrodes of solid oxide cells, but there are very limited reports on the formation and evolution of electrode/electrolyte interface of bismuth oxide-manganite composite electrode under the influence of electrochemical polarization. Herein, we report the effect of electrochemical polarization and direction of polarization current on the electrocatalytic performance and electrode/electrolyte interface of a (La0·8Sr0.2)0.95Mn0·95Pt0·05O3+δ-Er0.4Bi1·6O3 (LSMPt-ESB) composite oxygen electrode assembled on zirconia electrolyte. The cell with the LSMPt-ESB electrode produces outstanding performance for power generation and steam splitting, and it is stable without noticeable degradation during operation at 600 °C for 350 h in the fuel cell mode. The cathodic polarization induces in operando formation of electrode/electrolyte interface with observation of an Er-deficient LSMPt-ESB dense layer and Er-rich (Er,Bi,Mn)Ox particles on the zirconia electrolyte surface. This is different to the case of dwell under open circuit and in particular under anodic polarization conditions. The present study gains insights into the development of high performance, reliable bismuth oxide-manganite composite oxygen electrode for reduced temperature solid oxide cells.

Chromium nitride (CrN) coatings were deposited by magnetron sputtering onto Si(100) substrates. The coatings were then annealed at different temperatures (500–800 °C in steps of 100 °C) in air for 1 h. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), UV–Vis spectroscopy, nanoindentation tests and finite element modeling (FEM) were conducted in order to investigate their structural, morphological, optical and mechanical properties. XRD patterns show that the crystallinity of the CrN phase increases with the rise in annealing temperatures together with its preferred orientations along (111) and (200) diffraction planes. The lattice constants were slightly reduced from 4.19 to 4.11 nm at 800 °C. The lattice micorstrains and residual stresses were also reduced as the annealing temperatures rose as a result of reduced defects, dislocations and vacancies. Smooth grain-like surfaces with grain sizes ranging between ∼50 and 250 nm were confirmed by FESEM micrographs. XPS studies indicated the existence of Cr and N on the coating systems. Optical studies showed that with the rise in annealing temperature of up to 700 °C, the solar absorptance of CrN coatings is increased from 61% to 89% and slightly decreased at 800 °C, while the optical band-gap energy dropped from 2.62 to 1.38 eV and slightly increased to 1.48 eV at 800 °C. A gradual increase of dielectric constants of CrN films were realized with the subsequent annealing progression. Nanoindentation results indicated that as the annealing progresses, the hardness and elastic modulus values are lowered.

Rechargeable Zn–air battery is limited by the sluggish kinetics and poor durability of the oxygen catalysts. In this Research Article, a new bifunctional oxygen catalyst has been developed through embedding the ultrafine NiFeO nanoparticles (NPs) in a porous amorphous MnOx layer, in which the NiFeO-core contributes to the high activity for the oxygen evolution reaction (OER) and the amorphous MnOx–shell functions as active phase for the oxygen reduction reaction (ORR), promoted by the synergistic effect between the NiFeO core and MnOx shell. The synergistic effect is related to the electron drawing of NiFeO core from MnOx shell, which decreases the affinity and adsorption energy of oxygen on MnOx shell and significantly increases the kinetics of ORR. The electrocatalytic activity and durability of NiFeO@MnOx depends strongly on the NiFeO:MnOx ratio. NiFeO@MnOx with NiFeO:MnOx weight ratio of 1:0.8 shows the best performance for reversible ORR and OER, with a potential gap (ΔE) of 0.792 V to achieve a curr...

Phosphate poisoning of Pt electrocatalysts is one of the major barriers that constrains the performance of phosphoric acid-doped polybenzimidazole (PA/PBI) membrane fuel cells. Herein, we developed new atomically dispersed bimetallic FeCu coordinated with nitrogen-doped carbon nanotubes (FeCu/N-CNTs) as Pt-free oxygen reduction reaction (ORR) electrocatalysts. The cell with FeCu/N-CNTs cathodes delivers a peak power density of 302 mWcm−2 at 230℃, similar to that using Pt/C electrocatalysts (1 mgPt cm−2) but with a much better stability. In contrast to phosphate poisoning of Pt/C, FeCu/N-CNTs show PA enhanced activities. DFT calcualtions indicate that phosphate promotion effect results from the stronger binding of phosphate on Cu sites, which decreases the activation energy barrier for the cleavage of the O2 double bond and provides local protons to facilitate the proton-coupled electron transfer ORR. The results also show that FeCu/N-CNTs have a much better activity for ORR as comapre to Fe single atom catalysts coordinated with nitrogen-doped carbon nanotubes, Fe/N-CNTs. This study demonstrates the promising potential of bimetallic FeCu/N-CNTs as true Pt-free, highly active and durable cathodes for PA/PBI based high temperature polymer electrolyte fuel cells.

Carbon materials are promising alternatives to noble metal catalysts for oxygen reduction reactions (ORR) in energy conversion devices. Here we report hierarchically porous carbon microspheres with a trace amount of encapsulated cobalt as highly active and stable electrocatalysts for the ORR under wide pH values ranged from high alkaline to high acidic conditions. We use renewable natural date pulp as the carbon precursor and a facile hydrothermal carbonization method with in situ formed recyclable cobalt as a template for the synthesis. These catalysts yield competitive catalytic activity (a small Tafel slope of 53 mV dec-1) as well as superb durability and methanol tolerance compared to the benchmark Pt/C catalyst in alkaline electrolyte. Even under harsh acidic conditions, the catalysts deliver a satisfactory catalytic performance and good stability, indicating their extensive applicability. This performance is mainly attributed to the rich surface defects and the hierarchically porous structure that provide abundant active sites for the ORR. In situ formed cobalt nanoparticles are critical to the creation of the abundant mesopores, high specific surface area, and catalytically active defect sites over the carbon material. The encapsulated cobalt residual further enhances the ORR activity of the catalysts, while having a negligible effect on the cost due to its trace level (0.2 at.%).

The practical application of single atom catalysts (SACs) is constrained by the low achievable loading of single metal atoms. Here, nickel SACs stabilized on a nitrogen-doped carbon nanotube structure (NiSA-N-CNT) with ultrahigh Ni atomic loading up to 20.3 wt % have been successfully synthesized using a new one-pot pyrolysis method employing Ni acetylacetonate (Ni(acac)2) and dicyandiamide (DCD) as precursors. The yield and formation of NiSA-N-CNT depends strongly on the Ni(acac)2/DCD ratio and annealing temperature. Pyrolysis at 350 and 650 °C led to the formation of Ni single atom dispersed melem and graphitic carbon nitride (Ni-melem and Ni-g-C3N4). Transition from a stacked and layered Ni-g-C3N4 structure to a bamboo-shaped tubular NiSA-N-CNT structure most likely occurs via a solid-to-solid curling or rolling-up mechanism, thermally activated at temperatures of 700–900 °C. Extended X-ray absorption fine structure (EXAFS) experiments and simulations show that Ni single atoms are stabilized in the N-C...

Unreliable energy supply and environmental pollution are two major concerns of the human society in this century. Herein, we report a rational approach on preparation of hierarchically-structured cobalt-carbon composites with tunable properties for a number of applications. A facile hydrothermal treatment of cobalt nitrate and sucrose results in the formation of a metallic cobalt-amorphous carbon composite with cobalt nanospheres anchored homogenously on an amorphous carbon substrate. Tuning the calcination conditions in air will generate either a metallic cobalt-cobalt oxide core-shell structure with magnetism or a fully oxidized Co3O4 composite. The different materials are demonstrated as anodes for lithium-ion batteries (LIBs) and catalysts for advanced oxidation-based wastewater remediation. A fully oxidized composite (FC@CS, fully oxidized Co loaded on carbon spheres) as a LIB anode exhibits superior electrochemical performance, possessing a high reversible capacity, high initial columbic efficiency, outstanding cycling performance and excellent rate capability. The anode performance is superior to most reported Co3O4-based electrodes. Meanwhile, the partially oxidized composite (PC@CS, partially oxidized Co loaded on carbon spheres) functions as an efficient and stable catalyst for removal of phenol via peroxymonosulfate (PMS) activation, which is demonstrated via electron paramagnetic resonance (EPR) and quenching experiments for generation of radicals. More importantly, the recycled PC@CS can be further applied as a LIBs anode after full oxidation regeneration, performing comparably to FC@CS. This FC@CS → PC@CS → FC@CS transformation provides an innovative approach for efficient material synthesis, recycling and application.

Further to previous work on a seawater ligand mimetic calibration system for the electroanalysis of iron(III) in seawater using the iron chalcogenide glass ion-selective electrode (ISE), this study utilized alternative blends of synthetic ligands, in order to fine-tune and optimize the calibration response characteristics of this sensor for the electroanalysis of free iron(III) in seawater. Herein, an alternative calibration system (ACS) was derived using a mixture of 10 −4 M iron(III) chloride, 10 −4 M ethylenediaminetetraacetic acid (EDTA), 10 −3 M copper(II) sulphate, 5 × 10 −3 M ethylenediamine (EN) and 0.60 M sodium chloride yielding a Nernstian response of about 30 mV decade −1 . The electroanalysis of free iron(III) in seawater using the ACS generated a free iron(III) level commensurate with the predicted organic and inorganic speciation of iron(III) in seawater. Furthermore, electrochemical impedance spectroscopy (EIS), synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy have demonstrated that the surface reaction processes of this membrane in the ACS are comparable to those experienced in a natural seawater matrix. Ultimately, this study demonstrated that the ACS can mimic the surface chemistry and concomitant potentiometric response characteristics of the iron(III) sensor in seawater, enabling reliable electroanalyses of free iron(III) in seawater.

Despite the tremendous potential applications of hollow micro/nanostructures, their composition has been limited to mainly single chemical compounds. Inspired by recent innovations in the areas of metal organic frameworks (MOFs) and nanocoating, here, we report the rational synthesis of mesoporous ZnTiO3/TiO2 hollow polyhedra (MZTHP) obtained by hydrothermal treatment of zeolitic imidazolate framework-8 (ZIF-8)@TiO2 core–shell polyhedral particles. The subsequent calcination of these particles caused phase transformation from TiO2 to ZnTiO3 and eventually induced the formation of Zn2TiO4. In addition, the fabrication of these hollow structures revealed a way for the preparation of hollow polyhedral photocatalysts with Pt nanoparticles deposited onto their external surface (PHS-1) or encapsulated inside their hollow structures (PHS-2). Importantly, these two types of Pt-decorated nanoparticles are shown to exhibit an improved yet distinctly different performance for photocatalytic hydrogen production, highlighting that the photocatalytic activity correlates with the Pt location and dispersion.

Single-atom catalysts (SACs) are attracting significant attention due to their exceptional catalytic performance and stability. However, the controllable, scalable, and efficient synthesis of SACs remains a significant challenge. Herein, a new and versatile seeding approach is reported to synthesize SACs supported on different 2D materials such as graphene, boron nitride (BN), and molybdenum disulfide (MoS2). This method is demonstrated on the synthesis of Ni, Co, Fe, Cu, Ag, Pd single atoms as well as binary atoms of Ni and Cu codoped on 2D support materials with the mass loading of single atoms in the range of 2.8-7.9 wt%. In particular, the applicability of the new seeding strategy in electrocatalysis is demonstrate on nickel SACs supported on graphene oxide (SANi-GO), exhibiting excellent catalytic performance for electrochemical CO2 reduction reaction with a turnover frequency of 325.9 h(-1) at a low overpotential of 0.63 V and high selectivity of 96.5% for CO production. The facile, controllable, and scalable nature of this approach in the synthesis of SACs is expected to open new research avenues for the practical applications of SACs.

This paper presents the results from the investigation of arsenopyrite oxidation via mechano-chemical activation, using a stirred mill. Water and hydrogen peroxide were chosen as the lixiviant and oxidant, respectively, and maintained at a relatively low temperature (50 °C). The milling media size, mill speed, slurry percent solids and amount of H2O2 added were all kept constant throughoust these experiments. The only operational variable for this investigation was the milling time, which results in increasing levels of specific energy provided by the mill. The products of activated arsenopyrite are characterised in terms of phase composition, particulate and structural characteristics, along with reactivity. Mechano-chemical activation of arsenopyrite under oxidizing conditions shows a maximum dissolution of around 9 wt% for iron and 7 wt% for arsenic after 2 h of milling. After 3 h of milling, the main phase present is found to be amorphous in nature.

Iron single atom catalysts (Fe SACs) are the best‐known nonprecious metal (NPM) catalysts for the oxygen reduction reaction (ORR) of polymer electrolyte membrane fuel cells (PEMFCs), but their practical application has been constrained by the low Fe SACs loading (2 nanoparticle‐doped phosphoric acid/polybenzimidazole (PA/PBI/SiO2) composite membrane cells utilizing a FeSA‐G cathode with Fe SAC loading of 0.3 mg cm−2 delivers a peak power density of 325 mW cm−2 at 230 °C, better than 313 mW cm−2 obtained on the cell with a Pt/C cathode at a Pt loading of 1 mg cm−2. The cell with FeSA‐G cathode exhibits superior stability at 230 °C, as compared to that with Pt/C cathode. Our results provide a new approach to developing practical NPM catalysts to replace Pt‐based catalysts for fuel cells.

Two N-donor-functionalised ionic liquids (ILs), 1-ethyl-1,4-dimethylpiperazinium bis(trifluoromethylsulfonyl)amide (1) and 1-(2-dimethylaminoethyl)-dimethylethylammonium bis(trifluoromethylsulfonyl)amide (2), were synthesised and their electrochemical and transport properties measured. The data were compared with the benchmark system, N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (3). Marked differences in thermal and electrochemical stability were observed between the two tertiary-amine-functionalised salts and the non-functionalised benchmark. The former are up to 170 K and 2 V less stable than the structural counterpart lacking a tertiary amine function. The ion self-diffusion coefficients (Di ) and molar conductivities (Λ) are higher for the IL with an open-chain cation (2) than that with a cyclic cation (1), but less than that with a non-functionalised, heterocyclic cation (3). The viscosities (η) show the opposite behaviour. The Walden [Λ[proportionality](1/η)(t) ] and Stokes-Einstein [Di /T)[proportionality](1/η)(t) ] exponents, t, are very similar for the three salts, 0.93-0.98 (±0.05); that is, the self-diffusion coefficients and conductivity are set by η. The Di for 1 and 2 are the same, within experimental error, at the same viscosity, whereas Λ for 1 is approximately 13% higher than that of 2. The diffusion and molar conductivity data are consistent, with a slope of 0.98±0.05 for a plot of ln(ΛT) against ln(D+ +D- ). The Nernst-Einstein deviation parameters (Δ) are such that the mean of the two like-ion VCCs is greater than that of the unlike ions. The values of Δ are 0.31, 0.36 and 0.42 for 3, 1 and 2, respectively, as is typical for ILs, but there is some subtlety in the ion interactions given 2 has the largest value. The distinct diffusion coefficients (DDC) follow the order D(d)__ < D(d)++ < D(d)+_, as is common for [Tf2N](-) salts. The ion motions are not correlated as in an electrolyte solution: instead, there is greater anti-correlation between the velocities of a given anion and the overall ensemble of anions in comparison to those for the cationic analogue, the anti-correlation for the velocities of which is in turn greater than that for a given ion and the ensemble of oppositely charged ions, an observation that is due to the requirement for the conservation of momentum in the system. The DDC also show fractional SE behaviour with t~0.95.

Further to previous work on the ion-selective electrode (ISE) comprising a poly(3,4-ethylenedioxythiophene:poly(styrene sulfonate) [PEDOT : PSS] solid-contact (SC) and a plasticised polyvinyl chloride (PVC) membrane that led to blurring of interference fringes in neutron reflectometry (NR) data, the lipophilic polymethyl methacrylate/polydecyl methacrylate (PMMA-PDMA) copolymer ISE membrane was used to provide high quality NR data that is relatively free of interfacial roughening and unequivocal information on the uptake of water in this important SC ISE. The outcomes revealed that the hydrophobic PMMA-PDMA membrane remains free of absorbed water, while the underlying the PEDOT : PSS SC absorbs water, swelling and changing its neutron scattering properties.

An easy to fabricate and versatile cell that can be used with a variety of electrochemical techniques, also meeting the stringent requirement for undertaking cyclic voltammetry under transient conditions in in situ electrocrystallization studies and total external reflection X-ray analysis, has been developed. Application is demonstrated through an in situ synchrotron radiation-grazing incidence X-ray diffraction (SR-GIXRD) characterization of electrocrystallized cadmium (II)-tetracyanoquinodimethane material, Cd(TCNQ)2, from acetonitrile (0.1 mol dm−3 [NBu4][PF6]). Importantly, this versatile cell design makes SR-GIXRD suitable for almost any combination of total external reflection X-ray analysis (e.g., GIXRF and GIXRD) and electrochemical perturbation, also allowing its application in acidic, basic, aqueous, non-aqueous, low and high flow pressure conditions. Nevertheless, the cell design separates the functions of transient voltammetry and SR-GIXRD measurements, viz., voltammetry is performed at high flow rates with a substantially distended window to minimize the IR (Ohmic) drop of the electrolyte, while SR-GIXRD is undertaken using stop-flow conditions with a very thin layer of electrolyte to minimize X-ray absorption and scattering by the solution.

This paper reports on three-dimensional synchrotron radiation/Fourier transform-infrared microspectroscopy (SR/FT-IRM) imaging studies of water inclusions at the buried interface of solid-contact-ion-selective electrodes (SC-ISEs). It is our intention to describe a nondestructive method that may be used in surface studies of the buried interfaces of materials, especially multilayers of polymers. Herein, we demonstrate the power of SR/FT-IRM for studying water inclusions at the buried interfaces of SC-ISEs. A poly(methyl methacrylate)-poly(decyl methacyrlate) [PMMA-PDMA] copolymer revealed the presence of micrometer sized inclusions of water at the gold/membrane interface, while a coupling of a hydrophobic solid contact of poly(3-octylthiophene 2,5-diyl) (POT) prevented the accumulation of water at the buried interface. A similar study with a poly (3,4-ethylenedioxythiophene)/poly (styrenesulfonate) [PEDOT/PSS] solid contact also revealed an absence of distinct micrometer-sized pools of water; however, there were signs of absorption of water accompanied by swelling of the PEDOT/PSS underlayer, and these membrane zones are enriched with respect to water.

Single-atom catalysts (SACs) are the smallest entities for catalytic reactions with projected high atomic efficiency, superior activity, and selectivity; however, practical applications of SACs suffer from a very low metal loading of 1-2 wt%. Here, a class of SACs based on atomically dispersed transition metals on nitrogen-doped carbon nanotubes (MSA-N-CNTs, where M = Ni, Co, NiCo, CoFe, and NiPt) is synthesized with an extraordinarily high metal loading, e.g., 20 wt% in the case of NiSA-N-CNTs, using a new multistep pyrolysis process. Among these materials, NiSA-N-CNTs show an excellent selectivity and activity for the electrochemical reduction of CO2 to CO, achieving a turnover frequency (TOF) of 11.7 s-1 at -0.55 V (vs reversible hydrogen electrode (RHE)), two orders of magnitude higher than Ni nanoparticles supported on CNTs.

The use of perovskite materials as anion‐based intercalation pseudocapacitor electrodes has received significant attention in recent years. Notably, these materials, characterized by high oxygen vacancy concentrations, do not require high surface areas to achieve a high energy storage capacity as a result of the bulk intercalation mechanism. This study reports that reduced PrBaMn2O6–δ (r‐PBM), possessing a layered double perovskite structure, exhibits ultrahigh capacitance and functions as an excellent oxygen anion‐intercalation‐type electrode material for supercapacitors. Formation of the layered double perovskite structure, as facilitated by hydrogen treatment, is shown to significantly enhance the capacitance, with the resulting r‐PBM material demonstrating a very high gravimetric capacitance of 1034.8 F g−1 and an excellent volumetric capacitance of ≈2535.3 F cm−3 at a current density of 1 A g−1. The resultant formation of a double perovskite crystal oxide with a specific layered structure leads to the r‐PBM with a substantially higher oxygen diffusion rate and oxygen vacancy concentration. These superior characteristics show immense promise for their application as oxygen anion‐intercalation‐type electrodes in pseudocapacitors.

The observation of a multi-step stripping process at high positive potentials is reported for aluminium electrodeposition from a solution of AlCl3 in the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide. Cyclic voltammograms recorded on an aluminium-coated boron-doped diamond electrode revealed complex oxidative behaviour, suggesting that a passive layer forms on the freshly deposited aluminium that hinders electro-oxidation. High positive potentials are required to induce chloride attack of the passive film, composed of Al-NTf2 compounds, and facilitate the rapid oxidation of the underlying aluminium metal. These results have important implications in bipolar-pulse electroplating and electrorefining applications where electrodissolution of aluminium is required. Keywords: Aluminium, Oxidation, Corrosion, Voltammetry, Ionic liquid, Electrodeposition

Aluminium electrodeposition on a boron-doped diamond (BDD) electrode was studied in the ionic liquid: 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C4mpyr][NTf2]. Cyclic voltammograms recorded on BDD electrodes in 1 m solutions of AlCl3 in [C4mpyr][NTf2] were compared with those recorded on Au, Al and glassy carbon (GC) electrodes. The BDD electrode exhibits similar voltammetric responses for Al electrodeposition as on metallic electrodes but without interferences from alloy formation or reaction of the electrode material. Conversely, nucleation and growth of Al is significantly more difficult on freshly abraded GC. The electrochemical stability and activity of BDD over a wide potential range make it a highly favourable surface for studying metal deposition at very negative potentials in ionic liquids. Keywords: Aluminium, Electrochemistry, Boron-doped diamond, Ionic liquid, Voltammetry

Solid contact (SC) ion selective electrodes (ISEs) utilizing thin films of poly(34 ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and plasticized poly(vinylchloride) (PVC) have been produced using a spin casting procedure. This study was carried out with a view of characterizing this popular and well known SC ISE using a series of complementary surface analysis techniques. This work revealed that PEDOT: PSS prevents the separation of an undesirable water layer at the buried interface of this SC ISE due to the high miscibility of water in the hydrophilic PEDOT: PSS layer. The lack of a clearly defined and molecularly sharp buried interface prohibits the formation of a distinct water layer presumably by eliminating sites that promote the accumulation of water. This outcome is important to the chemical sensor community since it provides further insights into the compatibility of sensor components in SC ISEs.

This study aimed to develop a novel approach for the production of analytically robust and miniaturized polymeric ion sensors that are vitally important in modern analytical chemistry (e.g., clinical chemistry using single blood droplets, modern biosensors measuring clouds of ions released from nanoparticle-tagged biomolecules, laboratory-on-a-chip applications, etc.). This research has shown that the use of a water-repellent poly(methyl methacrylate)/poly(decyl methacrylate) (PMMA/PDMA) copolymer as the ion-sensing membrane, along with a hydrophobic poly(3-octylthiophene 2,5-diyl) (POT) solid contact as the ion-to-electron transducer, is an excellent strategy for avoiding the detrimental water layer formed at the buried interface of solid-contact ion-selective electrodes (ISEs). Accordingly, it has been necessary to implement a rigorous surface analysis scheme employing electrochemical impedance spectroscopy (EIS), in situ neutron reflectometry/EIS (NR/EIS), secondary ion mass spectrometry (SIMS), and small-angle neutron scattering (SANS) to probe structurally the solid-contact/membrane interface, so as to identify the conditions that eliminate the undesirable water layer in all solid-state polymeric ion sensors. In this work, we provide the first experimental evidence that the PMMA/PDMA copolymer system is susceptible to water "pooling" at the interface in areas surrounding physical imperfections in the solid contact, with the exposure time for such an event in a PMMA/PDMA copolymer ISE taking nearly 20 times longer than that for a plasticized poly(vinyl chloride) (PVC) ISE, and the simultaneous use of a hydrophobic POT solid contact with a PMMA/PDMA membrane can eliminate totally this water layer problem.

Aluminium electrodeposition is demonstrated from a thermally degraded ionic liquid solution. NMR and voltammetric analyses established that Al(3+) reduction was remarkably similar to that in non-degraded IL solutions suggesting that the electroactive metal-containing species was unaffected by heat treatment. Electron microscopy revealed a significant grain refinement of the deposited metal.

The in situ electrocrystallization of zinc tetracyanoquinodimethane (TCNQ) has been explored using synchrotron radiation-grazing incidence X-ray diffraction (SR-GIXRD) at potentials in the region of the cyclic voltammetric peak where reduction of TCNQ to TCNQ– occurs at a Pt electrode in acetonitrile (0.1 M [NBu4][PF6]) solution containing Zn(NO3)2·6H2O. The in situ SR-GIXRD data along with ex situ IR and Raman spectroscopy results all confirmed the formation of the kinetically favoured phase of Zn[TCNQ]2(H2O)2 as the product.