Overpotential

About: Overpotential is a research topic. Over the lifetime, 16474 publications have been published within this topic receiving 616632 citations.

Toward Full Exposure of “Active Sites”: Nanocarbon Electrocatalyst with Surface Enriched Nitrogen for Superior Oxygen Reduction and Evolution Reactivity

Abstract: The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play a decisive role for the efficiency of fuel cells and metal-air batteries. The nitrogen doped carbon materials with low cost and long durability are potential catalysts to replace precious metal catalyst for oxygen electrochemistry; however, the unexposed active sites induced by the bulk dopant atoms are hardly accessible and consequently scarcely contribute to the catalytic property. In this study, carbon nanotubes (CNTs) are selected as the platform to demonstrate the potential of full exposure of active sites' at the surface. Novel N-doped carbon coaxial nanocables with the pristine CNTs as the core and the N-doped carbon layers as the shell are proposed. The accessible and efficient utilization of the integrated nitrogen atoms enriched on the surface, together with the undestroyed intact inner walls, render the electrocatalyst much enhanced electrocatalytic activity and high electrical conductivity of 3.3 S cm(-1), therefore, N-doped nanocables afford higher oxygen reduction current, approximate to 51 mV positively shift onset potential, low peroxide generation, as well as lower overpotential and higher current for oxygen evoluation reaction.

Identifying active surface phases for metal oxide electrocatalysts: a study of manganese oxide bi-functional catalysts for oxygen reduction and water oxidation catalysis

Abstract: Progress in the field of electrocatalysis is often hampered by the difficulty in identifying the active site on an electrode surface. Herein we combine theoretical analysis and electrochemical methods to identify the active surfaces in a manganese oxide bi-functional catalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). First, we electrochemically characterize the nanostructured α-Mn2O3 and find that it undergoes oxidation in two potential regions: initially, between 0.5 V and 0.8 V, a potential region relevant to the ORR and, subsequently, between 0.8 V and 1.0 V, a potential region between the ORR and the OER relevant conditions. Next, we perform density function theory (DFT) calculations to understand the changes in the MnOx surface as a function of potential and to elucidate reaction mechanisms that lead to high activities observed in the experiments. Using DFT, we construct surface Pourbaix and free energy diagrams of three different MnOx surfaces and identify 1/2 ML HO* covered Mn2O3 and O* covered MnO2, as the active surfaces for the ORR and the OER, respectively. Additionally, we find that the ORR occurs through an associative mechanism and that its overpotential is highly dependent on the stabilization of intermediates through hydrogen bonds with water molecules. We also determine that OER occurs through direct recombination mechanism and that its major source of overpotential is the scaling relationship between HOO* and HO* surface intermediates. Using a previously developed Sabatier model we show that the theoretical predictions of catalytic activities match the experimentally determined onset potentials for the ORR and the OER, both qualitatively and quantitatively. Consequently, the combination of first-principles theoretical analysis and experimental methods offers an understanding of manganese oxide oxygen electrocatalysis at the atomic level, achieving fundamental insight that can potentially be used to design and develop improved electrocatalysts for the ORR and the OER and other important reactions of technological interest.

Highly Efficient CO2 Electroreduction on ZnN4 -based Single-Atom Catalyst.

Abstract: The electrochemical reduction reaction of carbon dioxide (CO2RR) to carbon monoxide (CO) is the basis for the further synthesis of more complex carbon-based fuels or attractive feedstock. Single-atom catalysts have unique electronic and geometric structures with respect to their bulk counterparts, thus exhibiting unexpected catalytic activities. A nitrogen-anchored Zn single-atom catalyst is presented for CO formation from CO2RR with high catalytic activity (onset overpotential down to 24 mV), high selectivity (Faradaic efficiency for CO (FECO ) up to 95 % at -0.43 V), remarkable durability (>75 h without decay of FECO ), and large turnover frequency (TOF, up to 9969 h-1 ). Further experimental and DFT results indicate that the four-nitrogen-anchored Zn single atom (Zn-N4 ) is the main active site for CO2RR with low free energy barrier for the formation of *COOH as the rate-limiting step.

Dynamic oxygen adsorption on single-atomic Ruthenium catalyst with high performance for acidic oxygen evolution reaction.

Abstract: Achieving active and stable oxygen evolution reaction (OER) in acid media based on single-atom catalysts is highly promising for cost-effective and sustainable energy supply in proton electrolyte membrane electrolyzers. Here, we report an atomically dispersed Ru1-N4 site anchored on nitrogen-carbon support (Ru-N-C) as an efficient and durable electrocatalyst for acidic OER. The single-atom Ru-N-C catalyst delivers an exceptionally intrinsic activity, reaching a mass activity as high as 3571 A gmetal−1 and turnover frequency of 3348 O2 h−1 with a low overpotential of 267 mV at a current density of 10 mA cm−2. The catalyst shows no evident deactivation or decomposition after 30-hour operation in acidic environment. Operando synchrotron radiation X-ray absorption spectroscopy and infrared spectroscopy identify the dynamic adsorption of single oxygen atom on Ru site under working potentials, and theoretical calculations demonstrate that the O-Ru1-N4 site is responsible for the high OER activity and stability. Monitoring catalyst structural changes under working conditions is crucial for understanding how catalysts operate. Here, authors examine single-atom Ru electrocatalyst by operando synchrotron spectroscopies to identify the catalytic mechanism during the acidic oxygen evolution reaction.

Molybdenum Carbide-Embedded Nitrogen-Doped Porous Carbon Nanosheets as Electrocatalysts for Water Splitting in Alkaline Media.

Abstract: Molybdenum carbide (Mo2C) based catalysts were found to be one of the most promising electrocatalysts for hydrogen evolution reaction (HER) in acid media in comparison with Pt-based catalysts but were seldom investigated in alkaline media, probably due to the limited active sites, poor conductivity, and high energy barrier for water dissociation. In this work, Mo2C-embedded nitrogen-doped porous carbon nanosheets (Mo2C@2D-NPCs) were successfully achieved with the help of a convenient interfacial strategy. As a HER electrocatalyst in alkaline solution, Mo2C@2D-NPC exhibited an extremely low onset potential of ∼0 mV and a current density of 10 mA cm–2 at an overpotential of ∼45 mV, which is much lower than the values of most reported HER electrocatalysts and comparable to the noble metal catalyst Pt. In addition, the Tafel slope and the exchange current density of Mo2C@2D-NPC were 46 mV decade–1 and 1.14 × 10–3 A cm–2, respectively, outperforming the state-of-the-art metal-carbide-based electrocatalysts in ...