Self-construction of pea-like Cu/Cu2S Mott-Schottky electrocatalyst for the oxygen evolution reaction

The speed of the oxygen evolution reaction seriously affects the hydrogen production efficiency of water electrolysis. Hence it is crucial to develop efficient and durable OER electrocatalysts. Construction of heterojunction catalysts is also one of the strategies to develop efficient catalysts. In this paper, a pea-like Cu/Cu₂S–C3 Mott?Schottky electrocatalyst was self-constructed by vapor deposition, while CF (copper foam) was used as substrate material and copper source, and thiourea was served as sulfur source. The built-in electric field is formed at the metal-semiconductor interface, which endows it with promising electrocatalytic performance. As the working electrode, the overpotentials of Cu/Cu₂S–C3 required to reach the current density of 10 and 50 mA cm^?2 were about 170 and 335 mV. The impact of the Mott-Schottky structure on the catalyst was also reflected in stability. The i-t tests of the sample Cu/Cu₂S–C3 were carried out under 10 and 60 mA cm^?2 and performed well.     

Anodic corrosion of heteroatom doped graphene oxide supports and its influence on the electrocatalytic oxygen evolution reaction

Transition metal-based electrocatalysts supported on carbon substrates face the challenges of anodic corrosion of carbon during oxygen evolution reaction at high oxidation potential. The role of electrophilic functional groups (carbonyl, pyridinic, thiol, etc.) incorporated in graphene oxide has been studied towards the anodic corrosion resistance. Heteroatom functionalized carbon supports possess modified electronic properties, surface oxygen content, and hydrophilicity, which are crucial in governing electrochemical corrosion in the alkaline oxidative environment. Evidently, electron-withdrawing groups in NGO support (pyridinic, cyano, nitro, etc) and its lower oxygen content impart maximum corrosion resistance and anodic stability in comparison to the other sulfur-doped and co-doped graphene oxide support. In this report, we establish the baseline evaluation of carbon-supported OER electrocatalysts by a systematic analysis of activity and substrate corrosion resistance. The result of this study establishes the role of surface composition of the doped supports while for designing a stable, corrosion-resistant OER electrocatalyst.     

One-step synthesis of Co2P/N-P co-doped porous carbon composites derived from soybean derivatives as acidic and alkaline HER electrocatalysts

Developing inexpensive and efficient electrocatalysts for hydrogen evolution reaction (HER) in both acidic and alkaline mediums is of great significance to the hydrogen energy industry. Hereby, we prepared a mixture of precursors with homogeneous composition by using the chelating ability of soybean protein isolate (C and N source) and phytic acid (dopant and phosphating agent) with cobalt ions, and achieved one-step synthesis and construction of Co₂P/N–P co-doped porous carbon composite by carbonization at 800 °C. The as-synthesized Co₂P/NPPC-800 electrocatalyst exhibits low HER overpotentials of 121 and 125 mV at 10 mA cm^?2 in 0.5 M H₂SO₄ and 1.0 M KOH, which are close to those of the commercial Pt/C catalyst. Additionally, the NPPC substrate surrounding the Co₂P could diminish the corrosion during the HER, and Co₂P/NPPC-800 displays good stability and durability. Furthermore, this work offers a convenient synthesis strategy for phosphide/doped porous carbon composites in other electrochemical energy technologies.     

Petal-like NiCoP sheets on 3D nitrogen-doped carbon nanofiber network as a robust bifunctional electrocatalyst for water splitting

Searching high-active, stable and abundant bifunctional catalysts to replace noble metals for hydrogen and oxygen evolution reactions (HER and OER) is desired. Herein, petal-like NiCoP sheets were synthesized on carbon paper covered with a 3D nitrogen-doped carbon nanofiber network (NiCoP/CNNCP) by a simple hydrothermal process followed by phosphorization. The HER overpotential in 0.5 M H₂SO₄ and OER overpotential in 1 M KOH of the NiCoP/CNNCP electrode only required 55 mV and 260 mV to drive a current density of 10 mA cm^?2, respectively, which was comparable or even better than most nickel-and cobalt-based phosphide catalysts. The overall water-splitting electrolyzer with an asymmetric electrolyte system assembled using NiCoP/CNNCP as bifunctional electrodes required an extremely low cell voltage of 1.04 V to achieve a current density of 10 mA cm^?2, which was much lower than almost all alkaline electrolysis systems.     

锡量子点制备及其电催化还原二氧化碳产甲酸性能

锡基材料在自然界含量丰富、价格低廉, 在电催化还原CO₂制液体燃料反应中具有巨大潜力。但是较低的产物选择性和较差的稳定性限制了其应用。本工作制备的锡量子点电催化剂(Sn-QDs), 具有高效、高稳定性和高选择性的电催化还原CO₂产HCOOH活性。Sn-QDs的平均颗粒尺寸仅为2~3 nm, 结晶性良好。小的颗粒尺寸增大了电化学活性面积(ECSA), Sn-QDs的ECSA约为锡颗粒的4.4倍。ECSA增大以及CO₂还原反应动力学加速, 促进了CO₂电化学转化。在-1.0 V (vs RHE)下, Sn-QDs/CN催化剂的HCOOH法拉第效率(FE_HCOOH)达到95%, 并且在宽约0.5 V的电势范围内能够保持在83%以上。此外, Sn-QDs/CN可以在24 h内保持良好的电化学稳定性。     

Engineering Silver-Enriched Copper Core-Shell Electrocatalysts to Enhance the Production of Ethylene and C2+ Chemicals from Carbon Dioxide at Low Cell Potentials

Copper catalysts are widely studied for the electroreduction of carbon dioxide (CO₂) to value-added hydrocarbon products. Controlling the surface composition of copper nanomaterials may provide the electronic and structural properties necessary for carbon-carbon coupling, thus increasing the Faradaic efficiency (FE) towards ethylene and other multi-carbon (C₂₊) products. Synthesis and catalytic study of silver-coated copper nanoparticles (Cu@Ag NPs) for the reduction of CO₂ are presented. Bimetallic CuAg NPs are typically difficult to produce due to the bulk immiscibility between these two metals. Slow injection of the silver precursor, concentrations of organic capping agents, and gas environment proved critical to control the size and metal distribution of the Cu@Ag NPs. The optimized Cu@Ag electrocatalyst exhibited a very low onset cell potential of −2.25 V for ethylene formation, reaching a FE towards C₂₊ products (FE_C2+) of 43% at −2.50 V, which is 1.0 V lower than a reference Cu catalyst to reach a similar FE_C2+. The high ethylene formation at low potentials is attributed to enhanced C C coupling on the Ag enriched shell of the Cu@Ag electrocatalysts. This study offers a new catalyst design towards increasing the efficiency for the electroreduction of CO₂ to value-added chemicals.     

Synthesis and characterization of transition metal mixed oxide doped graphene embedded durable electrocatalyst for hydrogen evolution reaction

A promising electrocatalyst containing variable percentage of V₂O₅–TiO₂ mixed oxide in graphene oxide support was prepared by embedding the catalyst on Cu substrate through facile electroless Ni–Co–P plating for hydrogen evolution reaction. The solvothermal decomposition method was opted for tuning the crystalline characteristics of prepared material. The optimized mixed oxide was well characterized, active sites centres were identified and explained by X-ray diffraction, high resolution tunnelling electron microscopy, scanning electron microscopy coupled with energy dispersive X-ray and X-ray photon spectroscopy analysis. The structural and electronic characteristics of material was done by fourier transform infrared spectroscopy and the electrochemical behaviour of the prepared material was evaluated by using Tafel plot, electrochemical impedance analysis, linear sweep voltammetry, open circuit analysis and chronoamperometry measurements. The results show the enhanced catalytic activity of Ni–Co–P than pure Ni–P plate, due to synergic effect. Moreover, the prepared mixed oxide incorporated Ni–Co–P plate has a high activity towards HER with low over potential of 101 mV, low Tafel slope of 36 mVdec^?1, high exchange current density of 9.90 × 10^?2 Acm^?2.     

Improved formic acid oxidation using electrodeposited Pd–Cd electrocatalysts in sulfuric acid solution

In the present research, nanostructured Pd–Cd alloy electrocatalysts with different compositions were produced using the electrodeposition process. The morphology of the samples was studied by scanning electron microscopy analysis. Also, the elemental composition of the samples was determined by energy-dispersive X-ray spectroscopy and elemental mapping tests. Tafel polarization and electrochemical impedance spectroscopy methods were employed to determine the electrochemical corrosion properties of the synthesized samples in a solution containing 0.5 M sulfuric acid and 0.1 M formic acid. The linear sweep voltammetry, cyclic voltammetry, and chronoamperometry techniques were also employed to evaluate the electrocatalytic activity of prepared samples toward the oxidation of formic acid. In this respect, the influence of some factors such as formic acid and sulfuric acid concentrations and also potential scan rate was investigated. Compared to the pure Pd sample, the Pd–Cd samples were more reactive for the oxidation of formic acid. Besides, the sample with a lower amount of Pd (Pd_1·3Cd) demonstrated much higher electrocatalytic activity than the Pd_7·1Cd and Pd_2·1Cd samples. The observed high mass activity of 15.06 A mg^?1_Pd for the Pd_1·3Cd sample which is 21.1 times higher than Pd/C is an interesting result of this study.