Overpotential

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

Universality in Oxygen Reduction Electrocatalysis on Metal Surfaces

Abstract: In this work, we extend the activity volcano for oxygen reduction from the face-centered cubic (fcc) metal (111) facet to the (100) facet. Using density functional theory calculations, we show that the recent findings of constant scaling between OOH* and OH* holds on the fcc metal (100) facet, as well. Using this fact, we show the existence of a universal activity volcano to describe oxygen reduction electrocatalysis with a minimum overpotential, ηmin = 0.37 ± 0.1 V. Specifically, we find that the (100) facet of Pt is found to bind oxygen intermediates too strongly and is not active for oxygen reduction reaction (ORR). In contrast, Au(100) is predicted to be more active than Au(111) and comparable in activity to Pt alloys. Using this activity volcano, we further predict that Au alloys that bind OH more strongly could display improved ORR activity on the (100) facet. We carry out a computational search over candidate alloys and suggest that alloying Au with early transition metals could lead to materials t...

Electrochemical and photoelectrochemical investigation of water oxidation with hematite electrodes

Abstract: Atomic layer deposition (ALD) was utilized to deposit uniform thin films of hematite (α-Fe2O3) on transparent conductive substrates for photocatalytic water oxidation studies. Comparison of the oxidation of water to the oxidation of a fast redox shuttle allowed for new insight in determining the rate limiting processes of water oxidation at hematite electrodes. It was found that an additional overpotential is needed to initiate water oxidation compared to the fast redox shuttle. A combination of electrochemical impedance spectroscopy, photoelectrochemical and electrochemical measurements were employed to determine the cause of the additional overpotential. It was found that photogenerated holes initially oxidize the electrode surface under water oxidation conditions, which is attributed to the first step in water oxidation. A critical number of these surface intermediates need to be generated in order for the subsequent hole-transfer steps to proceed. At higher applied potentials, the behavior of the electrode is virtually identical while oxidizing either water or the fast redox shuttle; the slight discrepancy is attributed to a shift in potential associated with Fermi level pinning by the surface states in the absence of a redox shuttle. A water oxidation mechanism is proposed to interpret these results.

Nest-like NiCoP for Highly Efficient Overall Water Splitting

Abstract: The investigation of high-efficiency nonprecious electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of great significance for renewable energy technologies. Here, we provide a successive hydrothermal, oxidation, and phosphidation method to fabricate a 3D nest-like ternary NiCoP/carbon cloth (CC) electrocatalyst with superior catalytic activity and stability toward HER/OER. Nest-like NiCoP/CC requires overpotentials of 44 and 62 mV to reach the current density of 10 mA cm–2 in acidic and alkaline media, respectively, toward HER. For OER, the NiCoP/CC exhibits high active and durable performance with an overpotential of 242 mV at current density of 10 mA cm–2 in alkaline solutions. Furthermore, the practical application of NiCoP/CC as a bifunctional catalyst for overall water splitting reaction yields current densities of 10 and 100 mA cm–2 at 1.52 and 1.77 V, respectively.

Amorphous Metallic NiFeP: A Conductive Bulk Material Achieving High Activity for Oxygen Evolution Reaction in Both Alkaline and Acidic Media

Abstract: The intrinsic catalytic activity at 10 mA cm-2 for oxygen evolution reaction (OER) is currently working out at overpotentials higher than 320 mV. A highly efficient electrocatalyst should possess both active sites and high conductivity; however, the loading of powder catalysts on electrodes may often suffer from the large resistance between catalysts and current collectors. This work reports a class of bulk amorphous NiFeP materials with metallic bonds from the viewpoint of electrode design. The materials reported here perfectly combine high macroscopic conductivity with surface active sites, and can be directly used as the electrodes with active sites toward high OER activity in both alkaline and acidic electrolytes. Specifically, a low overpotential of 219 mV is achieved at the geometric current density 10 mA cm-2 in an alkaline electrolyte, with the Tafel slope of 32 mV dec-1 and intrinsic overpotential of 280 mV. Meanwhile, an overpotential of 540 mV at 10 mA cm-2 is attained in an acidic electrolyte and stable for over 30 h, which is the best OER performance in both alkaline and acidic media. This work provides a different angle for the design of high-performance OER electrocatalysts and facilitates the device applications of electrocatalysts.

Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption

Abstract: The efficiency with which renewable fuels and feedstocks are synthesized from electrical sources is limited at present by the sluggish oxygen evolution reaction (OER) in pH-neutral media. We took the view that generating transition-metal sites with high valence at low applied bias should improve the activity of neutral OER catalysts. Here, using density functional theory, we find that the formation energy of desired Ni4+ sites is systematically modulated by incorporating judicious combinations of Co, Fe and non-metal P. We therefore synthesized NiCoFeP oxyhydroxides and probed their oxidation kinetics with in situ soft X-ray absorption spectroscopy (sXAS). In situ sXAS studies of neutral-pH OER catalysts indicate ready promotion of Ni4+ under low overpotential conditions. The NiCoFeP catalyst outperforms IrO2 and retains its performance following 100 h of operation. We showcase NiCoFeP in a membrane-free CO2 electroreduction system that achieves a 1.99 V cell voltage at 10 mA cm–2, reducing CO2 into CO and oxidizing H2O to O2 with a 64% electricity-to-chemical-fuel efficiency. Water oxidation is key to the production of chemical fuels from electricity. Now, guided by theory, NiCoFeP oxyhydroxide catalysts have been developed that require an overpotential lower than that required by IrO2. In situ soft X-ray absorption studies of neutral-pH NiCoFeP catalysts indicate formation of Ni4+, which is favourable for water oxidation.