Ruthenium Clusters Modification Carbon Layer-Encapsulated NiCoP Nanoneedles as Advanced Electrocatalyst for Efficient Seawater Splitting Application.

Developing efficient and durable electrocatalyst for seawater splitting is crucial in hydrogen production. Herein, a multi-scale design strategy was employed to fabricate ruthenium clusters modification carbon layer-encapsulated nickel-cobalt-phosphorus (Ru/C/NiCoP) nanoneedles electrocatalyst supported on nickel foam (NF). We demonstrated that Ru/C/NiCoP/NF exhibited exceptional oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performances, with low overpotential, Tafel slope and superior stability. Furthermore, the electrocatalytic mechanism of Ru/C/NiCoP was elucidated through the combination of ex-situ and in-situ characterizations, along with comprehensive electrochemical tests. Strikingly, Ru clusters and the carbon layer engendered robust electronic interaction reaction, accelerated the charge transfer rate, provided more active sites, and enhanced intrinsic catalytic activity, thus substantially promoting the OER kinetics and HER reaction steps as well as stability. In addition, the two-electrode system constructed with Ru/C/NiCoP/NF achieved current density of 10 mA cm-2 in both pure water and seawater at ultra-low potential of 1.46/1.47 V, with Faraday efficiency close to 100%. Even at higher current density of 100 mA cm-2, the required driving voltage remained low at 1.75/1.77 V, maintaining stable operation for 150 h, outperforming most reported non-noble catalysts. This innovative strategy provides facile and versatile approach for developing advanced electrocatalysts in seawater electrolysis application.

Research Progress on Ni-based Electrocatalysts for Electrochemical Reduction of Nitrogen to Ammonia.

The electrochemical NRR to synthesize ammonia is considered as a promising method due to its approvable advantages of zero-pollution emission, feasible reaction proceedings, good safety and easy management. The multiple efforts have been devoted to the exploration of earth-abundant-element-based nanomaterials as high-efficiency electrocatalysts for realizing their industrial applications. Among these, the Ni-based nanomaterials is prioritized as an attractive non-noble-metal electrocatalysts for catalyzing NRR because they are earth-abundance and exceedingly easy to synthesize as well as also delivers the potential of high electrocatalytic activity and durability. In this review, after briefly elucidating the underlying mechanisms of NRR during the electrochemical process, we systematically sum up the recent research progress in representative Ni-based electrocatalysts, including monometallic Ni-based nanomaterials, bimetallic Ni-based nanomaterials, polymetallic Ni-based nanomaterials, etc. In particular, we discuss the effects of physicochemical properties, such as phases, crystallinity, morphology, composition, defects, heteroatom doping, and strain engineering, on the comprehensive performance of the abovementioned electrocatalysts, with the aim of establishing the nanostructure-function relationships of the electrocatalysts. In addition, the promising directions of Ni-based electrocatalysts for NRR are also pointed out and highlighted. The generic approach in this review may expand the frontiers of NRR and provides the inspiration for developing high-efficiently Ni-based electrocatalysts.

Heteronuclear Dual Metal Atom Electrocatalysts for Water-Splitting Reactions.

Hydrogen is considered a promising substitute for traditional fossil fuels because of its widespread sources, high calorific value of combustion, and zero carbon emissions. Electrocatalytic water-splitting to produce hydrogen is also deemed to be an ideal approach; however, it is a challenge to make highly efficient and low-cost electrocatalysts. Single-atom catalysts (SACs) are considered the most promising candidate to replace traditional noble metal catalysts. Compared with SACs, dual-atom catalysts (DACs) are capable of greater attraction, including higher metal loading, more versatile active sites, and excellent catalytic activity. In this review, several general synthetic strategies and structural characterization methods of DACs are introduced, and recent experimental advances in water-splitting reactions are discussed. The authors hope that this review provides insights and inspiration to researchers regarding DACs in electrocatalytic water-splitting.

Construction and Application of an Electrochemical Sensor for Determination of D-Penicillamine Based on Modified Carbon Paste Electrode.

D-penicillamine (D-PA) is a sulfur-containing drug that has been used for various health conditions. However, like any medication, overdosing on D-PA can have adverse effects and may require additional treatment. Therefore, developing simple and sensitive methods for sensing D-PA can play a crucial role in improving its efficacy and reducing its side effects. Sensing technologies, such as electrochemical sensors, can enable accurate and real-time measurement of D-PA concentrations. In this work, we developed a novel electrochemical sensor for detecting D-PA by modifying a carbon paste electrode (CPE) with a multi-walled carbon nanotube-Co3O4 nanocomposite, benzoyl-ferrocene (BF), and ionic liquid (IL) (MWCNT-Co3O4/BF/ILCPE). Cyclic voltammetry (CV), differential pulse voltammetry (DPV), and chronoamperometry (CHA) were employed to explore the electrochemical response of D-PA on the developed sensor, the results of which verified a commendable electrochemical performance towards D-PA. Under optimized conditions, the developed sensor demonstrated a rapid response to D-PA with a linear dynamic range of 0.05 µM-100.0 µM, a low detection limit of 0.015 µM, and a considerable sensitivity of 0.179 µA µM-1. Also, the repeatability, stability, and reproducibility of the MWCNT-Co3O4/BF/ILCPE sensor were studied and showed good characteristics. In addition, the detection of D-PA in pharmaceutical and biological matrices yielded satisfactory recoveries and relative standard deviation (RSD) values.

Precise Anchoring of Fe Sites by Regulating Crystallinity of Novel Binuclear Ni-MOF for Revealing Mechanism of Electrocatalytic Oxygen Evolution.

Bimetallic metal-organic framework (BMOF) exhibits better electrocatalytic performance than mono-MOF, but deciphering the precise anchoring of foreign atoms and revealing the underlying mechanisms at the atomic level remains a major challenge. Herein, a novel binuclear NiFe-MOF with precise anchoring of Fe sites is synthesized. The low-crystallinity (LC)-NiFe0.33 -MOF exhibited abundant unsaturated active sites and demonstrated excellent electrocatalytic oxygen evolution reaction (OER) performance. It achieved an ultralow overpotential of 230 mV at 10 mA cm-2 and a Tafel slope of 41 mV dec-1 . Using a combination of modulating crystallinity, X-ray absorption spectroscopy, and theoretical calculations, the accurate metal sequence of BMOF and the synergistic effect of the active sites are identified, revealing that the adjacent active site plays a significant role in regulating the catalytic performance of the endmost active site. The proposed model of BMOF electrocatalysts facilitates the investigation of efficient OER electrocatalysts and the related catalytic mechanisms.

Potential Dominates Structural Recombination of Single Atom Mn Sites for Promoting Oxygen Reduction Reaction.

Single atom sites (SAS) often undergo structural recombination in oxygen reduction reaction (ORR), while the effect of valence state and reconstruction on active centers needs to be investigated thoroughly. Herein, the Mn-SAS catalyst with uniform and precise Mn-N4 configuration is rationally designed. We utilize operando synchrotron radiation to track the dynamic evolution of active centers during ORR. Under the applied potential, the structural evolution of Mn-N4 into Mn-N3 C and further into Mn-N2 C2 configurations is clarified. Simultaneously, the valence states of Mn are increased from +3.0 to +3.8 and then decreased to +3.2. When the potential is removed, the catalyst returned to its initial Mn+3.0 -N4 configuration. Such successive evolutions optimize the electronic and geometric structures of active centers as evidenced by theory calculations. The evolved Mn+3.8 -N3 C and Mn+3.2 -N2 C2 configurations respectively adjust the O2 adsorption and reduce the energy barrier of rate-determining step. Thus, it can achieve an onset potential of 0.99 V, superior stability over 10,000 cycles, and a high turnover frequency of 1.59 s-1 at 0.85 VRHE. Our present work provides new insights into the construction of well-defined SAS catalysts by regulating the valence states and configurations of active centers.

Pencil-like Hollow Carbon Nanotubes Embedded CoP-V4P3 Heterostructures as a Bifunctional Catalyst for Electrocatalytic Overall Water Splitting.

Electrocatalytic water splitting is one of the most efficient ways of producing green hydrogen energy. The design of stable, active, and efficient electrocatalysts plays a crucial role in water splitting for achieving efficient energy conversion from electrical to hydrogen energy, aimed at solving the lingering energy crisis. In this work, CNT composites modified with CoP-V4P3 composites (CoVO-10-CNT-450P) were formed by carbonising a pencil-like precursor (Co3V2O8-H2O) and growing carbon nanotubes in situ, followed by in situ phosphorylation on the carbon nanotubes. In the HER electrocatalytic process, an overpotential of only 124 mV was exhibited at a current density of 10 mA cm-2. In addition, as an OER catalyst, a low overpotential of 280 mV was attained at a current density of 10 mA cm-2. Moreover, there was no noticeable change in the performance of the catalyst over a 90 h test in a continuous total water splitting experiment. The unique electronic structure and hollow carbon nanotube structure of CoVO-10-CNT-450P effectively increased the catalytic active sites, while also significantly improving the electrocatalytic activity. This work provides theoretical guidance for the design and synthetic route of high-performance non-precious metal electrocatalysts, and actively promotes the commercial application of electrochemical water splitting.

Co-based Catalysts for Selective H2 O2 Electroproduction via 2-electron Oxygen Reduction Reaction.

Electrochemical production of hydrogen peroxide (H2 O2 ) via two-electron oxygen reduction reaction (ORR) process is emerging as a promising alternative method to the conventional anthraquinone process. To realize high-efficiency H2 O2 electrosynthesis, robust and low cost electrocatalysts have been intensively pursued, among which Co-based catalysts attract particular research interests due to the earth-abundance and high selectivity. Here, we provide a comprehensive review on the advancement of Co-based electrocatalyst for H2 O2 electroproduction. The fundamental chemistry of 2-electron ORR is discussed firstly for guiding the rational design of electrocatalysts. Subsequently, the development of Co-based electrocatalysts involving nanoparticles, compounds and single atom catalysts is summarized with the focus on active site identification, structure regulation and mechanism understanding. Moreover, the current challenges and future directions of the Co-based electrocatalysts are briefly summarized in this review.

Pr6O11: Temperature-Dependent Oxygen Vacancy Regulation and Catalytic Performance for Lithium-Oxygen Batteries.

Many challenges still exist in lithium-oxygen batteries (LOBs), particularly exploring an efficient catalyst to optimize the reaction pathway and regulate the Li2O2 nucleation. Pr6O11 has a unique 4f electronic structure and the highest oxygen ion mobility among rare earth oxides, exhibiting superior electronic, optical, and chemical properties. These unique properties might endow it with advanced catalytic activities for LOBs. This work reports two crystal forms of Pr6O11 as novel catalysts and regulates the oxygen vacancy (Vo) concentrations by feasible calcination. Thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) confirm the conversion from commercial Pr6O11 to cubic fluorite Pr6O11 and Vo-rich Pr6O11. Photographs, high-resolution transmission electron microscopy, selected area electron diffraction, XPS, and electron paramagnetic resonance robustly demonstrate the temperature-dependent evolution of Vo. Ex situ XPS, scanning electron microscopy, and electrochemical techniques are used to study the catalytic mechanism and electrochemical reversibility. It is found that an appropriate Vo concentration can boost O2 adsorption/desorption, accelerate electron transport, and reduce the reaction energy barrier. Vo-rich Pr6O11 optimizes the reaction pathway by offering an intermediate Li2-xO2 (with metalloid conductivity) and adjusting Li2O2 into vertically staggered nanoflakes, effectively avoiding the suffocation of the catalytic surface and presenting excellent capacity, cycling stability, and rate performance.

Detection and electrocatalytic mechanism of zearalenone using nanohybrid sensor based on copper-based metal-organic framework/magnetic Fe3O4-graphene oxide modified electrode.

A novel and simple strategy was proposed for the determination of ZEA in breakfast cereal, maize powder and rice flour using an electrochemical nanohybrid sensor based on copper-based metal-organic framework (Cu-MOF)/magnetic Fe3O4-graphene oxide (Fe3O4-GO) modified electrode fabricated by the layer-by-layer assembled technique. The synthesized Cu-MOF with high porosity favorably improved the effective surface area and the analytical performance of nanohybrid sensing electrode. The crafted sensor has large surface area, high electron transfer, and satisfactory efficiency. ZEA was electrochemically detected in a wide linear range from 159.2 to 2865.2 ng mL-1 with LOD of 23.14 ng mL-1 under the optimal conditions. Moreover, the electrocatalytic mechanism of ZEA oxidation was proposed by density functional theory (DFT). A favorable energetic interaction was presented when Cu-MOF adsorbed on Fe3O4-GO, and a small new band appeared on the Fermi level energy (Ef) that facilitated the electron transfer between bands.

Progress of carbon-based electrocatalysts for flexible zinc-air batteries in the past 5 years: recent strategies for design, synthesis and performance optimization.

The increasing popularity of wearable electronic devices has led to the rapid development of flexible energy conversion systems. Flexible rechargeable zinc-air batteries (ZABs) with high theoretical energy densities demonstrate significant potential as next-generation flexible energy devices that can be applied in wearable electronic products. The design of highly efficient and air-stable cathodes that can electrochemically catalyze both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are highly desirable but challenging. Flexible carbon-based catalysts for ORR/OER catalysis can be broadly categorized into two types: (i) self-supporting catalysts based on the in situ modification of flexible substrates; (ii) non-self-supporting catalysts based on surface coatings of flexible substrates. Methods used to optimize the catalytic performance include doping with atoms and regulation of the electronic structure and coordination environment. This review summarizes the most recently proposed strategies for the synthesis of designer carbon-based electrocatalysts and the optimization of their electrocatalytic performances in air electrodes. And we significantly focus on the analysis of the inherent active sites and their electrocatalytic mechanisms when applied as flexible ZABs catalysts. The findings of this review can assist in the design of more valuable carbon-based air electrodes and their corresponding flexible ZABs for application in wearable electronic devices.

Tunable Electrocatalytic Behavior of Sodiated MoS2 Active Sites toward Efficient Sulfur Redox Reactions in Room-Temperature Na-S Batteries.

Room-temperature (RT) sodium-sulfur (Na-S) batteries hold great promise for large-scale energy storage due to the advantages of high energy density, low cost, and resource abundance. The research progress on RT Na-S batteries, however, has been greatly hindered by the sluggish kinetics of the sulfur redox reactions. Herein, an elaborate multifunctional architecture, consisting of N-doped carbon skeletons and tunable MoS2 sulfiphilic sites, is fabricated via a simple one-pot reaction followed by in situ sulfurization. Beyond the physical confinement and chemical binding of polarized N-doped carbonaceous microflowers, the MoS2 active sites play a key role in catalyzing polysulfide redox reactions, especially the conversion from long-chain Na2 Sn (4 ≤ n ≤ 8) to short-chain Na2 S2 and Na2 S. Significantly, the electrocatalytic activity of MoS2 can be tunable via adjusting the discharge depth. It is remarkable that the sodiated MoS2 exhibits much stronger binding energy and electrocatalytic behavior compared to MoS2 sites, effectively enhancing the formation of the final Na2 S product. Consequently, the S cathode achieves superior electrochemical performance in RT Na-S batteries, delivering a high capacity of 774.2 mAh g-1 after 800 cycles at 0.2 A g-1 , and an ultrahigh capacity retention with a capacity decay rate of only 0.0055% per cycle over 2800 cycles.