Yolk-shell nanostructural Ni_2P/C composites as the high performance electrocatalysts toward urea oxidation

Highly active and low-cost catalytic electrodes for urea oxidation reaction(UOR) are always crucial for exploration of urea fuel cells.Herein,novel york-shell-structural Ni_2P/C na nosphere hybrids(Ni_2P/C-YS)are rationally constructed via a hydrothermal method and subsequent phosphidation treatment under different temperature ranging from 250℃ to 450℃ for UOR applications.In the in-situ constructed hollow york-shell structure,the coupling of conductive carbon materials and active Ni_2P allows numerous interfaces facilitating the electron transfer and thereby accelerating the catalytic kinetics.The results demonstrate that Ni_2P/C-YS-350 nanocomposite can boost the UOR process with a low potential of 1.366 V vs.RHE at a current density of 50 mA/cm~2 in alkaline electrolyte and afford the superior durability with negligible potential decay after 23 h.This study presents that the carbon coated Ni_2P hybrid with the optimized crystallinities and hollow york-shell configurations can be a promising candidate for application in urea fuel cells.     

Red-blood-cell like nitrogen-doped carbons with highly catalytic activity towards oxygen reduction reaction

A highly active nitrogen-doped catalyst with a unique red-blood-cell(RBC) like structure is reported for oxygen reduction reaction(ORR).The catalyst Fe,N-C@carbon-900 was prepared by pyrolysis of the polyaniline(PANl) and polystyrene(PS) composites with adsorption of ferric ion on the shell of sphere structure at 900℃.Fe,N-C@carbon-900 with a unique RBC-like structure provides plenty of catalytic sites combining the electrical conductivity of the carbon sphere with the catalytic activity of the nitrogen-doped layer.The four-electron reduction pathway is selected for the catalyst Fe,N-C@carbon-900.The catalyst exhibit the ORR E_(onset) at 0.87 V(potentials is versus to reversible hydrogen electrode(RHE)),E_(1/2) at 0.78 V and high diffusion-limiting current density(5.20mA/cm~2).Furthermore,this work indicates that both N and Fe accounted for high activity of the catalyst Fe,N-C@carbon-900 toward the oxygen reduction process.It is concluded that Fe and N exhibit synergistically promotion in the ORR activity for the catalyst Fe,N-C@carbon-900.We also provide a rational design of electrocatalysts with high ORR activity to further clarify the essential ORR sites of heteroatom doped carbon materials for fuel cells and metal-air battery applications.     

From Biomimicking to Bioinspired Design of Electrocatalysts for CO2 Reduction to C1 Products

The electrochemical reduction of CO₂ (CO₂RR) is a promising approach to maintain a carbon cycle balance and produce value-added chemicals. However, CO₂RR technology is far from mature, since the conventional CO₂RR electrocatalysts suffer from low activity (leading to currents <10 mA cm⁻² in an H-cell), stability (<120 h), and selectivity. Hence, they cannot meet the requirements for commercial applications (>200 mA cm⁻², >8000 h, >90 % selectivity). Significant improvements are possible by taking inspiration from nature, considering biological organisms that efficiently catalyze the CO₂ to various products. In this minireview, we present recent examples of enzyme-inspired and enzyme-mimicking CO₂RR electrocatalysts enabling the production of C₁ products with high faradaic efficiency (FE). At present, these designs do not typically follow a methodical approach, but rather focus on isolated features of biological systems. To achieve disruptive change, we advocate a systematic design methodology that leverages fundamental mechanisms associated with desired properties in nature and adapts them to the context of engineering applications.     

Chromium-Doped Nickel Oxide and Nickel Nitride Mediate Selective Electrocatalytic Oxidation of Sterol Intermediates Coupled with H2 Evolution

Replacing the oxygen evolution reaction (OER) with the thermodynamically favorable electrooxidation of organics is considered a promising approach for the simultaneous production of hydrogen (H₂) and high-value chemicals. However, exploring and optimizing efficient electrocatalysts remains a challenge for large-scale production of value-added steroid carbonyl and H₂. Herein, Cr-NiO/GF and Cr-Ni₃N/GF (GF: graphite felt) electrocatalysts were designed as anode and cathode for the production of steroid carbonyls and H₂, respectively. The cooperative Cr-NiO and ACT (4-acetamido-2,2,6,6-tetramethyl-1-piperidine-N-oxyl) electrocatalyst can be extended to the electrooxidation of a series of steroid alcohols to the corresponding aldehydes. Additionally, Cr-Ni₃N displays superior electrocatalytic activity for hydrogen evolution reaction (HER), with a low overpotential of 35 mV to deliver 10 mA cm⁻². Furthermore, the system coupled with anodic electrooxidation of sterol and cathodic HER exhibited excellent performance with high space-time yield of 48.85 kg m⁻³ h⁻¹ for steroid carbonyl and 1.82 L h⁻¹ for H₂ generation in a two-layer stacked flow cell. Density Functional Theory (DFT) calculations indicated that Cr doping effectively stabilizes ACTH on the NiO surface, and ACTH molecule could be captured via the ketonic oxygen interaction with Cr, resulting in excellent electrocatalytic activity. This work develops a novel approach to the rational design of efficient electrocatalysts for the simultaneous production of H₂ and large-scale value-added pharmaceutical carbonyl intermediates.     

Sulfur Changes the Electrochemical CO2 Reduction Pathway over Cu Electrocatalysts

Electrochemical CO₂ reduction to value-added chemicals or fuels offers a promising approach to reduce carbon emissions and alleviate energy shortage. Cu-based electrocatalysts have been widely reported as capable of reducing CO₂ to produce a variety of multicarbon products (e.g., ethylene and ethanol). In this work, we develop sulfur-doped Cu₂O electrocatalysts, which instead can electrochemically reduce CO₂ to almost exclusively formate. We show that a dynamic equilibrium of S exists at the Cu₂O-electrolyte interface, and S-doped Cu₂O undergoes in situ surface reconstruction to generate active S-adsorbed metallic Cu sites during the CO₂ reduction reaction (CO₂RR). Density functional theory (DFT) calculations together with in situ infrared absorption spectroscopy measurements show that the S-adsorbed metallic Cu surface can not only promote the formation of the *OCHO intermediate but also greatly suppress *H and *COOH adsorption, thus facilitating CO₂-to-formate conversion during the electrochemical CO₂RR.     

Synergistic Fe−Se Atom Pairs as Bifunctional Oxygen Electrocatalysts Boost Low-Temperature Rechargeable Zn-Air Battery

Herein, we successfully construct bifunctional electrocatalysts by synthesizing atomically dispersed Fe−Se atom pairs supported on N-doped carbon (Fe−Se/NC). The obtained Fe−Se/NC shows a noteworthy bifunctional oxygen catalytic performance with a low potential difference of 0.698 V, far superior to that of reported Fe-based single-atom catalysts. The theoretical calculations reveal that p-d orbital hybridization around the Fe−Se atom pairs leads to remarkably asymmetrical polarized charge distributions. Fe−Se/NC based solid-state rechargeable Zn-air batteries (ZABs−Fe−Se/NC) present stable charge/discharge of 200 h (1090 cycles) at 20 mA cm⁻² at 25 °C, which is 6.9 times of ZABs−Pt/C+Ir/C. At extremely low temperature of −40 °C, ZABs−Fe−Se/NC displays an ultra-robust cycling performance of 741 h (4041 cycles) at 1 mA cm⁻², which is about 11.7 times of ZABs−Pt/C+Ir/C. More importantly, ZABs−Fe−Se/NC could be operated for 133 h (725 cycles) even at 5 mA cm⁻² at −40 °C.     

Transition metal chalcogenides as emerging electrocatalysts for urea electrolysis

Urea electrolysis is an up-and-coming approach to realize sustainable energy-saving hydrogen fuel production and purification of urea-bearing wastes (e.g. urine, industrial wastewater). To attain a high urea electrolysis efficiency, high-performance electrocatalysts are highly required. Of late, transition metal (TM) chalcogenides-based materials are emerging as promising candidates for urea electrolysis. The catalytic performance of TM chalcogenides-based catalysts is optimized by tuning the internal/external characteristics, including nanostructure control, composition optimization, and heterostructuring. In this review, recent achievements in high-efficiency electrocatalysts based on TM chalcogenides for urea electrolysis are critically discussed. First, the electrochemistry of urea electrolysis is analyzed. Next, recent progress in TM chalcogenides-based electrocatalysts for urea electrolysis is detailed. The electrocatalyst design strategies are particularly elucidated, as well as the catalyst structure–performance correlation. Ultimately, perspectives on crucial scientific issues in this booming field are highlighted.     

基于金属氧化物材料的二氧化碳电催化还原

The CO₂ level in the atmosphere has been increasing since the industrial revolution owing to anthropogenic activities. The increased CO₂ level has led to global warming and also has detrimental effects on human beings. Reducing the CO₂ level in the atmosphere is urgent for balancing the carbon cycle. In this regard, reduction in CO₂ emission and CO₂ storage and usage are the main strategies. Among these, CO₂ usage has been extensively explored, because it can reduce the CO₂ level and simultaneously provide opportunities for the development in catalysts and industries to convert CO₂ as a carbon source for preparing valuable products. However, transformation of CO₂ to other chemicals is challenging owing to its thermodynamic and kinetic stabilities. Among the CO₂ utilization techniques, electrochemical CO₂ reduction (ECR) is a promising alternative because it is generally conducted under ambient conditions, and water is used as the economical hydrogen source. Moreover, ECR offers a potential route to store electrical energy from renewable sources in the form of chemical energy, through generation of CO₂ reduction products. To improve the energy efficiency and viability of ECR, it is important to decrease the operational overpotential and maintain large current densities and high product selectivities; the development of efficient electrocatalysts is a critical aspect in this regard. To date, many kinds of materials have been designed and studied for application in ECR. Among these materials, metal oxide-based materials exhibit excellent performance as electrocatalysts for ECR and are attracting increasing attention in recent years. Investigation of the mechanism of reactions that involve metallic electrocatalysts has revealed the function of trace amount of oxidized metal species—it has been suggested that the presence of metal oxides and metal-oxygen bonds facilitates the activation of CO₂ and the subsequent formation and stabilization of the reaction intermediates, thereby resulting in high efficiency and selectivity of the ECR. Although the stability of metal oxides is a concern as they are prone to reduction under a cathodic potential, the catalytic performance of metal oxide-based catalysts can be maintained through careful designing of the morphology and structure of the materials. In addition, introducing other metal species to metal oxides and fabricating composites of metal oxides and other materials are effective strategies to achieve enhanced performance in ECR. In this review, we summarize the recent progress in the use of metal oxide-based materials as electrocatalysts and their application in ECR. The critical role, stability, and structure-performance relationship of the metal oxide-based materials for ECR are highlighted in the discussion. In the final part, we propose the future prospects for the development of metal oxide-based electrocatalysts for ECR.     

Low-temperature plasma technology for electrocatalysis

The latest applications of plasma in energy storage and conversion are summarized here, including using it as the preparation and modification technology of the various electrocatalysts and the usage of it as the synthesis technology directly. Also, the challenges and outlook of plasma technology in energy storage and conversion were summarized, and the solutions and prospected its development in the future were present.     

XPS study of the state of iridium, platinum, titanium and oxygen in thermally formed IrO2+TiO2+PtOX films

Electrodes of nominal composition Ir_0.3Ti_(0.7−x)Pt_xO₂ (x=0; 0.4 and 0.7) have been prepared by thermal decomposition of mixtures of the chloride precursors. H₂PtCl₆ was used as Pt-precursor. A systematic study of the chemical composition and oxidation states of the elements of these electrodes was performed by XPS. XPS analysis showed that the surface of the PtO_x-containing coatings are Pt enriched. Additionally, XPS revealed that the Ir signals are almost absent from the spectra of PtO_x-containing electrodes, while the Ti signal is completely absent. On the basis of the XPS results it is possible to propose a model of the surface structure of these electrodes: the grains, composed almost exclusively of Ir+Pt, are Pt enriched and distributed in a matrix, which although having Ti in its composition, besides Ir and Pt, is also Pt enriched. This finding corroborates the electrochemical behaviour of these electrodes, which is characteristic of polycrystalline Pt.