Metastable Ni(I)-TiO _2-x Photocatalysts: Self-Amplifying H₂ Evolution from Plain Water without Noble Metal Co-Catalyst and Sacrificial Agent

Decoration of semiconductor photocatalysts with cocatalysts is generally done by a step-by-step assembly process. Here, we describe the self-assembling and self-activating nature of a photocatalytic system that forms under illumination of reduced anatase TiO2 nanoparticles in an aqueous Ni2+ solution. UV illumination creates in situ a Ni+/TiO2/Ti3+ photocatalyst that self-activates and, over time, produces H-2 at a higher rate. In situ X-ray absorption spectroscopy and electron paramagnetic resonance spectroscopy show that key to self-assembly and self-activation is the light-induced formation of defects in the semiconductor, which enables the formation of monovalent nickel (Ni+) surface states. Metallic nickel states, i.e., Ni-0, do not form under the dark (resting state) or under illumination (active state). Once the catalyst is assembled, the Ni+ surface states act as electron relay for electron transfer to form H-2 from water, in the absence of sacrificial species or noble metal cocatalysts.Web of Science14548261322612

Investigating the platinum electrode surface during Kolbe electrolysis of acetic acid

Platinum is commonly applied as the anode material for Kolbe electrolysis of carboxylic acids thanks to its superior performance. Literature claims that the formation of a barrier layer on the Pt anode in carboxylic acid electrolyte suppresses the competing oxygen evolution and promotes anodic decarboxylation. In this work, we show by using a combination of complementary in situ and ex situ surface sensitive techniques, that the presence of acetate ions also prevents the formation of a passive oxide layer on the platinum surface at high anodic potentials even in aqueous electrolyte. Furthermore, Pt dissolves actively under these conditions, challenging the technical implementation of Kolbe electrolysis. Future studies exploring the activity-structure-stability relation of Pt are required to increase the economic viability of Kolbe electrolysis

Deciphering the Exceptional Performance of NiFe Hydroxide for Oxygen Evolution Reaction in Anion Exchange Membrane Electrolyzer

Hydrogen production via water electrolysis with renewable electricity as input will be crucial for the coming defossilized energy age. Herein, we report an anion exchange membrane electrolyzer using Fe-doped Ni hydroxide as anode catalyst that is on par with proton exchange membrane electrolyzers in terms of performance, 2 A cm-2 at 2.046 V and 50 °C. We found that Fe-doping stabilizes the alfa-Ni(OH)2 phase which is key to ensure the fast Ni(OH)2/NiOOH redox transition and the subsequent fast reaction between Ni3+/4+ and the electrolyte (OH-), resulting in the excellent oxygen evolution reaction activity of Fe-doped Ni hydroxide. Spin-polarized DFT+U computations reveal that the local arrangement of Fe3+ with Ni3+/4+ plays a crucial role in enabling the high OER activity on (001) facet of this anode catalyst

Electrochemical Surface Area Quantification, CO2 Reduction Performance, and Stability Studies of Unsupported Three-Dimensional Au Aerogels versus Carbon-Supported Au Nanoparticles

The efficient scale-up of CO2-reduction technologies is a pivotal step to facilitate intermittent energy storage and for closing the carbon cycle. However, there is a need to minimize the occurrence of undesirable side reactions like H2 evolution and achieve selective production of value-added CO2-reduction products (CO and HCOO–) at as-high-as-possible current densities. Employing novel electrocatalysts such as unsupported metal aerogels, which possess a highly porous three-dimensional nanostructure, offers a plausible approach to realize this. In this study, we first quantify the electrochemical surface area of an Au aerogel (≈5 nm in web thickness) using the surface oxide-reduction and copper underpotential deposition methods. Subsequently, the aerogel is tested for its CO2-reduction performance in an in-house developed, two-compartment electrochemical cell. For comparison purposes, similar measurements are also performed on polycrystalline Au and a commercial catalyst consisting of Au nanoparticles supported on carbon black (Au/C). The Au aerogel exhibits a faradaic efficiency of ≈97% for CO production at ≈−0.48 VRHE, with a suppression of H2 production compared to Au/C that we ascribe to its larger Au-particle size. Finally, identical-location transmission electron microscopy of both nanomaterials before and after CO2-reduction reveals that, unlike Au/C, the aerogel network retains its nanoarchitecture at the potential of peak CO production.ISSN:2694-246

Highly Active Anode Electrocatalysts Derived from Electrochemical Leaching of Ru from Metallic Ir0.7Ru0.3 for Proton Exchange Membrane Electrolyzers

Hydrogen produced by water splitting is a promising solution for a sustained economy from renewable energy sources. Proton exchange membrane (PEM) electrolysis is the utmost suitable technology for this purpose, although the quest for low cost, highly active and durable catalysts is persistent. Here we develop a nanostructured iridium catalyst after electrochemically leaching ruthenium from metallic iridium-ruthenium, Ir0.7Ru0.3Ox (EC), and compare its physical and electrochemical properties to the thermally treated counterpart: Ir0.7Ru0.3O2 (TT). Ir0.7Ru0.3Ox (EC) shows an unparalleled 13-fold higher oxygen evolution reaction (OER) activity compared to the Ir0.7Ru0.3O2 (TT). PEM electrolyzer tests at 1 A cm-2 show no increase of cell voltage for almost 400 h, proving that Ir0.7Ru0.3Ox (EC) is one of the most efficient anodes so far developed