Single Cobalt Sites Dispersed in Hierarchically Porous Nanofiber Networks for Durable and High-Power PGM-Free Cathodes in Fuel Cells

Increasing catalytic activity and durability of atomically dispersed metal–nitrogen–carbon (M–N–C) catalysts for the oxygen reduction reaction (ORR) cathode in proton-exchange-membrane fuel cells remains a grand challenge. Here, a high-power and durable Co–N–C nanofiber catalyst synthesized through electrospinning cobalt-doped zeolitic imidazolate frameworks into selected polyacrylonitrile and poly(vinylpyrrolidone) polymers is reported. The distinct porous fibrous morphology and hierarchical structures play a vital role in boosting electrode performance by exposing more accessible active sites, providing facile electron conductivity, and facilitating the mass transport of reactant. The enhanced intrinsic activity is attributed to the extra graphitic N dopants surrounding the CoN₄ moieties. The highly graphitized carbon matrix in the catalyst is beneficial for enhancing the carbon corrosion resistance, thereby promoting catalyst stability. The unique nanoscale X-ray computed tomography verifies the well-distributed ionomer coverage throughout the fibrous carbon network in the catalyst. The membrane electrode assembly achieves a power density of 0.40 W cm⁻² in a practical H₂/air cell (1.0 bar) and demonstrates significantly enhanced durability under accelerated stability tests. The combination of the intrinsic activity and stability of single Co sites, along with unique catalyst architecture, provide new insight into designing efficient PGM-free electrodes with improved performance and durability.     

Bimetallic Phosphide Heterostructure Coupled with Ultrathin Carbon Layer Boosting Overall Alkaline Water and Seawater Splitting

Seawater electrolysis is promising for green hydrogen production but hindered by the sluggish reaction kinetics of both cathode and anode, as well as the detrimental chlorine chemistry environment. Herein, a self-supported bimetallic phosphide heterostructure electrode strongly coupled with an ultrathin carbon layer on Fe foam (C@CoP-FeP/FF) is constructed. When used as an electrode for the hydrogen and oxygen evolution reactions (HER/OER) in simulated seawater, the C@CoP-FeP/FF electrode shows overpotentials of 192 mV and 297 mV at 100 mA cm⁻², respectively. Moreover, the C@CoP-FeP/FF electrode enables the overall simulated seawater splitting at the cell voltage of 1.73 V to achieve 100 mA cm⁻², and operate stably during 100 h. The superior overall water and seawater splitting properties can be ascribed to the integrated architecture of CoP-FeP heterostructure, strongly coupled carbon protective layer, and self-supported porous current collector. The unique composites can not only provide enriched active sites, ensure prominent intrinsic activity, but also accelerate the electron transfer and mass diffusion. This work confirms the feasibility of an integration strategy for the manufacturing of a promising bifunctional electrode for water and seawater splitting.     

Self‐Assembled 3D Foam‐Like NiCo2O4 as Efficient Catalyst for Lithium Oxygen Batteries

A self‐assembled 3D foam‐like NiCo₂O₄ catalyst has been synthesized via a simple and environmental friendly approach, wherein starch acts as the template to form the unique 3D architecture. Interestingly, when employed as a cathode for lithium oxygen batteries, it demonstrates superior bifunctional electrocatalytic activities toward both the oxygen reduction reaction and the oxygen evolution reaction, with a relatively high round‐trip efficiency of 70% and high discharge capacity of 10 137 mAh g^?1 at a current density of 200 mA g^?1, which is much higher than those in previously reported results. Meanwhile, rotating disk electrode measurements in both aqueous and nonaqueous electrolyte are also employed to confirm the electrocatalytic activity for the first time. This excellent performance is attributed to the synergistic benefits of the unique 3D foam‐like structure and the intrinsically high catalytic activity of NiCo₂O₄.     

Fluorescence imaging of the heterogeneous reduction of oxygen

The reduction of oxygen at a variety of solid electrodes was spatially imaged using fluorescence microscopy. Hydroxide produced during electrolysis of oxygen converted the acid-base indicator, fluorescein, into its fluorescent form. Fluorescence intensity was collected as a function of potential at platinum, silver, and glassy carbon disk electrodes and tracked the faradaic current due to oxygen reduction at platinum electrodes. The ability to observe spatial variations in electron-transfer kinetics was demonstrated at a bimetallic electrode prepared from silver and platinum. Fluorescence imaging of oxygen reduction on silver electrodeposited on glassy carbon revealed the location and size of the silver deposits. Imaging of oxygen reduction at a ruthenium-graphite composite electrode demonstrated the ability to identify electrochemically active sites on a spatially complex surface.     

A High-Performance Hybrid Biofuel Cell with a Honeycomb-Like Ti3C2Tx/MWCNT/AuNP Bioanode and a ZnCo2@NCNT Cathode for Self-Powered Biosensing

This work focusses on developing a hybrid enzyme biofuel cell-based self-powered biosensor with appreciable stability and durability using murine leukemia fusion gene fragments (tDNA) as a model analyte. The cell consists of a Ti₃C₂T_x/multiwalled carbon nanotube/gold nanoparticle/glucose oxidase bioanode and a Zn/Co-modified carbon nanotube cathode. The bioanode uniquely exhibits strong electron transfer ability and a high surface area for the loading of 1.14 × 10⁻⁹ mol cm⁻² glucose oxidase to catalyze glucose oxidation. Meanwhile, the abiotic cathode with a high oxygen reduction reaction activity negates the use of conventional bioenzymes as catalysts, which aids in extending the stability and durability of the sensing system. The biosensor offers a 0.1 fm –1 nm linear range and a detection limit of 0.022 fm tDNA. Additionally, the biosensor demonstrates a reproducibility of ≈4.85% and retains ≈87.42% of the initial maximal power density after a 4-week storage at 4 °C, verifying a significantly improved long-term stability.     

Double perovskite oxides Sr2MMoO6 (M = Fe and Co) as cathode materials for oxygen reduction in alkaline medium

The oxygen reduction reaction (ORR) was studied on Sr₂MMoO₆ (M = Fe and Co) double perovskites, prepared by a solid-state reaction, in 0.5 M NaOH at 25 °C with a rotating disk electrode (RDE). The two oxide powders were characterized by X-ray diffraction, scanning electron microscopy and BET analysis. The electrochemical techniques considered are linear voltammetry, steady state polarization and ac impedance spectroscopy. The electrocatalysts (SFMO/C, SCMO/C) consisting of the double perovskite oxides and carbon (Vulcan XC-72) were mixed and spread out into a thin layer on a glassy carbon substrate. At room temperature, a significantly electrocatalytic activity is observed for both electrocatalysts. Compared to SFMO/C, the SCMO/C electrocatalyst was found to show a relatively high electrocatalytic activity for O₂ reduction, which agrees well with the results obtained using the ac impedance spectroscopy.     

Nonionic surfactant-templated mesoporous carbon as an electrocatalyst support for methanol oxidation

Two carbons were synthesized for use as platinum electrocatalyst supports for methanol oxidation. For both materials, furfuryl alcohol was used as the carbon precursor; however, one (CPEG) was made using poly ethylene glycol as the pore former, while the other (CSRF) was produced using Pluronic^® F127 as the soft template by organic–organic self-assembly. The CPEG and CSRF carbons were estimated from nitrogen physisorption experiments to be micro- and mesoporous, respectively. Platinum nanoparticles were deposited on each carbon as well as on Vulcan XC-72 carbon by the formic acid reduction method. The physicochemical properties of electrocatalysts were studied using X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy dispersive X-ray analysis (EDX), and their electrochemical features were examined using cyclic voltammetry, chronoamperometry, and impedance spectroscopy. It was found that higher methanol oxidation peak current densities as well as lesser charge transfer resistance at electrode/electrolyte interface were obtained for Pt supported on CSRF as compared to those on Vulcan XC-72 carbon, owing to the higher specific surface area and larger total pore volume (696 m² g⁻¹ and 0.60 cm³ g⁻¹, respectively) together with superior electrical conductivity of mesoporous CSRF. On the other hand, the lower surface area and pore volume of microporous CPEG substrate confined Pt nanoparticles deposition and thus made CPEG-supported Pt an inefficient methanol oxidation electrocatalyst.     

Ce Site in Amorphous Iron Oxyhydroxide Nanosheet toward Enhanced Electrochemical Water Oxidation

Iron oxyhydroxide has been considered an auspicious electrocatalyst for the oxygen evolution reaction (OER) in alkaline water electrolysis due to its suitable electronic structure and abundant reserves. However, Fe-based materials seriously suffer from the tradeoff between activity and stability at a high current density above 100 mA cm⁻². In this work, the Ce atom is introduced into the amorphous iron oxyhydroxide (i.e., CeFeO_xH_y) nanosheet to simultaneously improve the intrinsic electrocatalytic activity and stability for OER through regulating the redox property of iron oxyhydroxide. In particular, the Ce substitution leads to the distorted octahedral crystal structure of CeFeO_xH_y, along with a regulated coordination site. The CeFeO_xH_y electrode exhibits a low overpotential of 250 mV at 100 mA cm⁻² with a small Tafel slope of 35.1 mVdec⁻¹. Moreover, the CeFeO_xH_y electrode can continuously work for 300 h at 100 mA cm⁻². When applying the CeFeO_xH_y nanosheet electrode as the anode and coupling it with the platinum mesh cathode, the cell voltage for overall water splitting can be lowered to 1.47 V at 10 mA cm⁻². This work offers a design strategy for highly active, low-cost, and durable material through interfacing high valent metals with earth-abundant oxides/hydroxides.     

Electroanalytical properties and application of anthraquinone derivative-functionalized multiwalled carbon nanotubes nanowires modified glassy carbon electrode in the determination of dissolved oxygen

We herein report a simple, low cost and green preparation of nanowires of (anthraquinone-2-carboxylic acid/amino functionalized) multiwalled carbon nanotubes (HOOC-2-AQ/AMWCNTs) which has been further employed for the development of highly sensitive oxygen sensor. The prepared composite has been characterized by TEM and electrochemical studies. The glassy carbon electrode modified with composite shows an irreversible and good electrocatalytic activity for the reduction of oxygen. The reduction potential of the oxygen was shifted 460 mV towards the positive potential with this modified electrode as compared to bare glassy carbon electrode. The prepared material was stable with no leaching observed of the mediator. A linear response range of 0.2–6.8 mg L^?1, with a sensitivity of 5.0 μA L mg^?1 and a detection limit of 0.02 mg L^?1 were obtained with this sensor.     

Electrochemical and spectroscopic characterization of a Benzo[c]cinnoline electrografted platinum surface

In this work, a platinum surface was modified with benzo[c]cinnoline (BCC) to get new insight into the metal modification area. By potential scanning from + 0.4 V to - 0.8 V, the diazotized BCC was reduced electrochemically and grafted onto the platinum electrode surface to form benzo[c]cinnoline modified platinum electrode (Pt-BCC). Electrochemical reduction of benzo[c]cinnoline diazonium salt on the electrode surface yielded a relatively stable organic film. The introduction of BCC molecules onto the platinum surface was verified by cyclic voltammetry, electrochemical impedance spectroscopy, Raman spectroscopy and ellipsometry. The stability and the potential range of the Pt-BCC electrode were also studied.     

An Iron-Decorated Carbon Aerogel for Rechargeable Flow and Flexible Zn–Air Batteries

Mechanically stable and foldable air cathodes with exceptional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities are key components of wearable metal–air batteries. Herein, a directional freeze-casting and annealing approach is reported for the construction of a 3D honeycomb nanostructured, N,P-doped carbon aerogel incorporating in situ grown FeP/Fe₂O₃ nanoparticles as the cathode in a flexible Zn–air battery (ZAB). The aqueous rechargeable Zn–air batteries assembled with this carbon aerogel exhibit a remarkable specific capacity of 648 mAh g⁻¹ at a current density of 20 mA cm⁻² with a good long-term durability, outperforming those assembled with commercial Pt/C+RuO₂ catalyst. Furthermore, such a foldable carbon aerogel with directional channels can serve as a freestanding air cathode for flexible solid-state Zn–air batteries without the use of carbon paper/cloth and additives, giving a specific capacity of 676 mAh g⁻¹ and an energy density of 517 Wh kg⁻¹ at 5 mA cm⁻² together with good cycling stability. This work offers a new strategy to design and synthesize highly effective bifunctional air cathodes to be applied in electrochemical energy devices.     

Construction of multilayers of bare and Pd modified gold nanoclusters and their electrocatalytic properties for oxygen reduction

Abstract

Multilayers of gold nanoclusters (GNCs) coated with a thin Pd layer were constructed using GNCs modified with self-assembled monolayers (SAMs) of mercaptoundecanoic acid and a polyallylamine hydrochloride (PAH) multilayer assembly, which has been reported to act as a three-dimensional electrode. SAMs were removed from GNCs by electrochemical anodic decomposition and then a small amount of Pd was electrochemically deposited on the GNCs. The kinetics of the oxygen reduction reaction (ORR) on the Pd modified GNC/PAH multilayer assembly was studied using a rotating disk electrode, and a significant increase in the ORR rate was observed after Pd deposition. Electrocatalytic activities in alkaline and acidic solutions were compared both for the GNC multilayer electrode and Pd modified GNC electrode.     

Heteroatom Coordination Regulates Iron Single-Atom-Catalyst with Superior Oxygen Reduction Reaction Performance for Aqueous Zn-Air Battery

Platinum group metal (PGM)-free M-N-C catalysts have exhibited dramatic electrocatalytic performance and are considered the most promising candidate of the Pt catalysts in oxygen reduction reaction (ORR). However, the electrocatalytic performance of the M-N-C catalysts is still limited by their inferior intrinsic activity and finite active site density. Regulating the coordination environment and increasing the pore structure of the catalyst is an effective strategy to enhance the electrocatalytic performance of the M-N-C catalysts. In this work, the coordination environment and pore structure exquisitely regulated Fe-N-C catalyst exhibit excellent ORR activity and durability. With the enhanced intrinsic activity and increased active site density, the optimized Fe-N/S-C catalyst shows impressive ORR activity (E_1/2 = 0.904 V vs reversible hydrogen electrode (RHE)) and superior long-term durability in an alkaline medium. As the advanced physical characterization and theoretical chemistry methods illustrate, the S-modified Fe-N_x (Fe-N₃/S-C) moiety is confirmed as the improved active center for ORR, and the increased active site density further improved ORR efficiency. Based on the Fe-N/S-C cathode, a Zn-air battery is fabricated and shows superior power density (315.4 mW cm⁻²) and long-term discharge stability at 20 mA cm⁻². This work would open a new perspective to design atomically dispersed iron-metal site catalysts for advanced electro-catalysis.     

Nucleation and growth of copper particles on Pt and Pt/poly-3-methylthiophene modified electrode in presence of Cl complexing agent

The kinetics of electrochemical deposition of copper particles from Cu²⁺ solution on platinum and poly-3-methylthiophene modified platinum electrode was studied in potentiostatic conditions in presence of Cl⁻ anions. The complex behavior of current transients suggests that the deposition process involves several stages with different kinetics. Results obtained on platinum show that after an initial adsorption process, the copper deposition is accomplished through two different models: a three-dimensional nucleation and growth under diffusive control (3DPD model) and a progressive nucleation and two-dimensional growth (2DP model). The analysis of current transients recorded on platinum poly-3-methylthiophene modified electrode (Pt/PMT) shows a very different behavior. On Pt modified electrode a process of growth related to a semi-infinite diffusion to a planar surface was accompanied by two different mechanisms of nucleation and growth: a three-dimensional nucleation and growth with no diffusive control (3DP model) and an instantaneous nucleation with two-dimensional growth (2DP model).     

A Glucose Biosensor Based on Immobilization of Glucose Oxidase in Electropolymerized o-Aminophenol Film on Platinized Glassy Carbon Electrode

A high-performance amperometric glucose biosensor has been developed, based on immobilization of glucose oxidase in an electrochemically synthesized, nonconducting poly(o-aminophenol) film on a platinized glassy carbon electrode. The large microscopic surface area and porous morphology of the platinized glassy carbon electrode result in high enzyme loading, and the enzyme entrapped in the electrodeposited platinum microparticle matrix is stabler than that on a platinum disk electrode surface. The response current of the sensor is 20-fold higher than that of the sensor prepared with a platinum disk electrode of the same geometric area. The experiments showed that the high sensitivity of the sensor is due not only to the large microscopic area but also to the high efficiency of transformation of H(2)O(2) generated by enzymatic reaction to current signal on the platinized glassy carbon electrode. The response time of the sensor is <4 s, and its lifetime is >10 months.     

Rate-limiting steps of tyrosinase-modified electrodes for the detection of catechol

The response currents obtained for tyrosinase-modified Teflon/graphite, carbon paste, and solid graphite electrodes in the presence of catechol are analyzed primarily using rotating disk electrode experiments. The rate-limiting steps, such as the electrochemical reduction of o-quinones and the enzymatic reduction of oxygen as well as the enzymatic oxidation of catechol, are theoretically considered and experimentally demonstrated for the different electrode configurations.     

Growth of carbon nanotubes on aluminium foil for supercapacitors electrodes

A new approach for the preparation of carbon nanotubes (CNTs) electrode is proposed in the present work. Multi-walled carbon nanotubes (MWCNTs) were grown by chemical vapour deposition on aluminium strips pre-plated with a nickel thin film as the catalyst. The CNTs were characterized by scanning and transmission electron microscopy, Brunauer–Emmett–Teller surface area measurement and thermogravimetric analysis. The nickel-plated aluminium foil with a layer of CNTs was further characterized for an assessment of its electrochemical behaviour as electrode for supercapacitors. The specific capacitances of the electrode, as derived from cyclic voltammetry measurement at 0.1 V s⁻¹ scan rate, was found to be 54 and 79 F g⁻¹ in aqueous and organic electrolytes, respectively, in line with the highest reported values for either activated carbon or MWCNTs electrodes. Further evidence in support of the viability of the present approach for the preparation of a CNTs electrode was obtained from electrochemical impedance spectroscopy.     

三维石墨烯-碳纳米管复合材料的制备及其氧还原催化性能研究

采用化学气相沉积法（CVD）制备了硼、氮共掺杂三维石墨烯与碳纳米管复合的非金属电催化材料（B-N-G-CNT）。利用扫描电子显微镜（SEM）、能谱仪（EDS）、透射电子显微镜（TEM）对B-N-G-CNT的形貌、结构及成分进行了表征,结果显示：三维石墨烯－碳纳米管呈有序多孔网状结构,石墨烯与碳纳米管形成稳定的化学结合,具有质量高、缺陷少等优点。运用循环伏安法（CV）、旋转圆盘电极（RDE）、电流时间曲线（i-t curve）等手段测试了B-N-G-CNT在碱性介质中的氧还原电化学性能,结果表明：在浓度为0.1 mol·L-1 的KOH溶液中,B-N-G-CNT复合材料具有比 B-N-G更高的起始电位和半波势能,其电子转移数接近4电子;同时B-N-G-CNT比商业Pt/C具有更高的稳定性。     

Electrochemical reduction of noble metal compounds in ethylene glycol

The effect of temperature on both the electrochemical oxidation of pure ethylene glycol and the reduction of AuCl₄⁻ in ethylene glycol at a rotating disk glassy carbon electrode has been investigated using linear sweep voltammetry. As the temperature is increased from 25°C up to 60°C, ethylene glycol begins to oxidize at lower potentials, whereas the reduction potential of AuCl₄⁻ is independent of temperature. Reduction current densities, however, increase as temperature increases. Room temperature reduction of several noble metal species in ethylene glycol was also investigated. Metal reduction potentials at both a platinum and a glassy carbon electrodes follow the sequence: AuC1₄⁻>Ag⁺>PtC1₆²⁻>Pd(NH₃)₄²⁺. The oxidation potential of ethylene glycol at both electrodes was found to be more positive than the reduction potential of the gold, silver, platinum and palladium precursors. These results predict that the spontaneous formation of noble metal particles by chemical reduction with ethylene glycol is thermodynamically unfavorable at 25°C. Gold and silver particles, however, are easily prepared at room temperature using the polyol process, which is a redox based process for the preparation of finely divided metals by chemical reduction of the corresponding metal precursors with ethylene glycol. Since measured potentials are the sum of a thermodynamic and a kinetic contribution (the overpotential), metal reduction in the polyol process seems to be aided by the overpotential. Therefore, measured potentials have been correlated to the chemical conditions at which noble metal particles are synthesized in the polyol process. It was found that as the potential difference between ethylene glycol oxidation and metal reduction increases, both the reaction temperature and time needed for metal synthesis increases. These electrochemical results may contribute to have a better understanding of the fundamentals of the polyol process, and for optimizing such reaction parameters as temperature, time and solution chemistry.     

石墨化介孔碳包裹WC纳米粒子的构建及其氧还原性能研究

采用模板复型辅助的化学气相沉积法(CVD)成功制备出一种非贵金属的氧还原反应(ORR)催化剂材料—包裹碳化钨纳米粒子的石墨化介孔碳(WC/MG)复合物。制备的介孔结构WC/MG复合材料不仅具有高氧还原反应电化学催化活性, 还表现出良好的电化学稳定性。在O₂饱和的0.1 mol/L KOH电解质溶液中, 900℃制备的样品WC/ MG-900其半波电势(E_1/2)和极限电流密度仅比商用贵金属催化剂Pt/C分别低50 mV 和 0.2 mA/cm²。Koutecky- Levich曲线和旋转环盘电极实验均表明, 该介孔结构的WC/MG复合材料表现出近似4电子的ORR反应途径, 具有可与Pt/C催化剂相比拟的ORR催化活性, 以及比Pt/C更优越的电化学稳定性和耐甲醇性能, 使得该介孔结构WC/MG复合物在氧还原电极材料中表现出良好的应用前景。