Electrochemical reforming of ethanol with acetate Co-Production on nickel cobalt selenide nanoparticles

The energy efficiency of water electrolysis is limited by the sluggish reaction kinetics of the anodic oxygen evolution reaction (OER). To overcome this limitation, OER can be replaced by a less demanding oxidation reaction, which in the ideal scenario could be even used to generate additional valuable chemicals. Herein, we focus on the electrochemical reforming of ethanol in alkaline media to generate hydrogen at a Pt cathode and acetate as a co-product at a NiCoSe anode. We first detail the solution synthesis of a series of NiCoSe electrocatalysts. By adjusting the Ni/Co ratio, the electrocatalytic activity and selectivity for the production of acetate from ethanol are optimized. Best performances are obtained at low substitutions of Ni by Co in the cubic NiSe phase. Density function theory reveals that the Co substitution can effectively enhance the ethanol adsorption and decrease the energy barrier for its first step dehydrogenation during its conversion to acetate. However, we experimentally observe that too large amounts of Co decrease the ethanol-to-acetate Faradaic efficiency from values above 90% to just 50 %. At the optimized composition, the NiCoSe electrode delivers a stable chronoamperometry current density of up to 45 mA cm, corresponding to 1.2 A g, in a 1 M KOH + 1 M ethanol solution, with a high ethanol-to-acetate Faradaic efficiency of 82.2% at a relatively low potential, 1.50 V vs. RHE, and with an acetate production rate of 0.34 mmol cm h.This work was supported by the start-up funding at Chengdu University. It was also supported by the European Regional Development Funds and by the Spanish Ministerio de Economía y Competitividad through the project SEHTOP (ENE2016-77798-C4-3-R), MCIN/ AEI/10.13039/501100011033/ project, and NANOGEN (PID2020-116093RB-C43). X. Wang, C. Xing, X. Han, R. He, Z. Liang, and Y. Zhang are grateful for the scholarship from China Scholarship Council (CSC). X. Han and J. Arbiol acknowledge funding from Generalitat de Catalunya 2017 SGR 327. ICN2 acknowledges support from the Severo Ochoa Programme (MINECO, Grant no. SEV-2013-0295). IREC and ICN2 are funded by the CERCA Programme / Generalitat de Catalunya

Nickel iron diselenide for highly efficient and selective electrocatalytic conversion of methanol to formate

The electro-oxidation of methanol to formate is an interesting example of the potential use of renewable energies to add value to a biosourced chemical commodity. Additionally, methanol electro-oxidation can replace the sluggish oxygen evolution reaction when coupled to hydrogen evolution or to the electroreduction of other biomass-derived intermediates. But the cost-effective realization of these reaction schemes requires the development of efficient and low-cost electrocatalysts. Here, a noble metal-free catalyst, Ni1−xFexSe2 nanorods, with a high potential for an efficient and selective methanol conversion to formate is demonstrated. At its optimum composition, Ni0.75Fe0.25Se2, this diselenide is able to produce 0.47 mmol cm−2 h−1 of formate at 50 mA cm−2 with a Faradaic conversion efficiency of 99%. Additionally, this noble-metal-free catalyst is able to continuously work for over 50 000 s with a minimal loss of efficiency, delivering initial current densities above 50 mA cm−2 and 2.2 A mg−1 in a 1.0 m KOH electrolyte with 1.0 m methanol at 1.5 V versus reversible hydrogen electrode. This work demonstrates the highly efficient and selective methanol-to-formate conversion on Ni-based noble-metal-free catalysts, and more importantly it shows a very promising example to exploit the electrocatalytic conversion of biomass-derived chemicals.J.L. obtained International Postdoctoral Exchange Fellowship Program (Talent-Introduction program No. YJ20190126) in 2019 and is grateful for the project (2019M663468) funded by the China Postdoctoral Science Foundation. This work was supported from the UESTC start-up funding, the Recruitment Program of Thousand Youth Talents, and the Natural Science Foundation of China (22072013). It was also supported by the European Regional Development Funds and by the Spanish Ministerio de Economía y Competitividad through the project SEHTOP (ENE2016-77798-C4-3-R) and VALPEC (ENE2017-85087-C3). C.X., Y.Z., and T.Z. are grateful for the China Scholarship Council (CSC) for scholarship support. T.Z., and J.A. acknowledge funding from Generalitat de Catalunya 2017 SGR 327. ICN2 acknowledges support from the Severo Ochoa Programme (MINECO, Grant no. SEV-2013-0295). T.Z. has received funding from the CSC-UAB PhD scholarship program. M.C.S. has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 754510 (PROBIST) and the Severo Ochoa programme. IREC and ICN2 are funded by the CERCA Programme/Generalitat de Catalunya. Part of the present work has been performed in the framework of Universitat Autònoma de Barcelona Materials Science PhD program. J.L. is a Serra Húnter Fellow and is grateful to MICINN/FEDER RTI2018-093996-B-C31, GC 2017 SGR 128 and to ICREA Academia program.Peer reviewe

Improved water oxidation with metal oxide catalysts via a regenerable and redox-inactive ZnOxHy overlayer

We report a regenerable and redox-inactive ZnOxHy layer that was in situ deposited onto metal oxides MOz (M = Co, Fe, and Ni) in alkaline media containing [Zn(OH)4]2− species during water oxidation. An interface dipole was developed at the MOz/Zn interface, resulting in a decrease of the OER overpotential. Exemplified by the CoOz/ZnOxHy bilayer structure, it presented a 155 mV lower overpotential to deliver 10 mA cm−2 and long-term stability relative to the unmodified CoOz film

Efficient Alkaline Water Oxidation with a Regenerable Nickel Pseudo-Complex

Efficient and robust electrocatalysts are required for the oxygen evolution reaction (OER). Photosystem II-inspired synthetic transition metal complexes have shown promising OER activity in water-poor or mild conditions, yet challenges remain in the improvement of current density and performance stability for practical applications in alkaline electrolytes in contrast to solid-state oxide catalysts. Here, we report that a nickel pseudo-complex (bpy)zNiOxHy (bpy = 2,2′-bipyridine) catalyst, which bridges solid oxide and molecular catalysts, exhibits the highest OER activity among nickel-based catalysts with a turnover frequency of 1.1 s–1 at an overpotential of 0.30 volts, even outperforming iron-incorporated nickel (oxy)hydroxide under an identical nickel mass load. Benefiting from the strong coordination between bpy and nickel, this (bpy)zNiOxHy catalyst exhibits long-term stability in highly alkaline media at 1.0 mA cm–2 for over 200 h and at 20 mA cm–2 for over 60 h. Our findings indicate that dynamically coordinating a small amount of bpy in the catalyst layer efficiently sustains highly active nickel sites for water oxidation, demonstrating a general strategy for improving the activity of transition metal sites with active ligands beyond the incorporation of metal cations to form double-layered hydroxides

Non-covalent ligand-oxide interaction promotes oxygen evolution

Strategies to generate high-valence metal species capable of oxidizing water often employ composition and coordination tuning of oxide-based catalysts, where strong covalent interactions with metal sites are crucial. However, it remains unexplored whether a relatively weak “non-bonding” interaction between ligands and oxides can mediate the electronic states of metal sites in oxides. Here we present an unusual non-covalent phenanthroline-CoO2 interaction that substantially elevates the population of Co4+ sites for improved water oxidation. We find that phenanthroline only coordinates with Co2+ forming soluble Co(phenanthroline)2(OH)2 complex in alkaline electrolytes, which can be deposited as amorphous CoOxHy film containing non-bonding phenanthroline upon oxidation of Co2+ to Co3+/4+. This in situ deposited catalyst demonstrates a low overpotential of 216 mV at 10 mA cm−2 and sustainable activity over 1600 h with Faradaic efficiency above 97%. Density functional theory calculations reveal that the presence of phenanthroline can stabilize CoO2 through the non-covalent interaction and generate polaron-like electronic states at the Co-Co center

Electrophysiological correlation of the degree of self-reference effect.

The present study investigated neural correlations underlying the psychological processing of stimuli with various degrees of self-relevance. Event-related potentials were recorded for names that differ in their extent of relevance to the study participant. Participants performed a three-stimulus oddball task. ERP results showed larger P2 averaged amplitudes for highly self-relevant names than for moderately self-relevant, minimally self-relevant, and non-self-relevant names. N2 averaged amplitudes were larger for the highly self-relevant names than for the moderately self-relevant, minimally self-relevant, and non-self-relevant names. Highly self-relevant names elicited larger P3 averaged amplitudes than the moderately self-relevant names which, in turn, had larger P3 values than for minimally self-relevant names. Minimally self-relevant stimuli elicited larger P3 averaged amplitudes than non-self-relevant stimuli. These results demonstrate a degree effect of self-reference, which was indexed using electrophysiological activity

Nickel Iron Diselenide for Highly Efficient and Selective Electrocatalytic Conversion of Methanol to Formate

The electro-oxidation of methanol to formate is an interesting example of the potential use of renewable energies to add value to a biosourced chemical commodity. Additionally, methanol electro-oxidation can replace the sluggish oxygen evolution reaction when coupled to hydrogen evolution or to the electroreduction of other biomass-derived intermediates. But the cost-effective realization of these reaction schemes requires the development of efficient and low-cost electrocatalysts. Here, a noble metal-free catalyst, Ni1−xFexSe2 nanorods, with a high potential for an efficient and selective methanol conversion to formate is demonstrated. At its optimum composition, Ni0.75Fe0.25Se2, this diselenide is able to produce 0.47 mmol cm−2 h−1 of formate at 50 mA cm−2 with a Faradaic conversion efficiency of 99%. Additionally, this noble-metal-free catalyst is able to continuously work for over 50 000 s with a minimal loss of efficiency, delivering initial current densities above 50 mA cm−2 and 2.2 A mg−1 in a 1.0 m KOH electrolyte with 1.0 m methanol at 1.5 V versus reversible hydrogen electrode. This work demonstrates the highly efficient and selective methanol-to-formate conversion on Ni-based noble-metal-free catalysts, and more importantly it shows a very promising example to exploit the electrocatalytic conversion of biomass-derived chemicals

Nickel iron diselenide for highly efficient and selective electrocatalytic conversion of methanol to formate

Altres ajuts: IREC and ICN2 are funded by the CERCA Programme/Generalitat de Catalunya. Part of the present work has been performed in the framework of Universitat Autònoma de Barcelona Materials Science PhD program. J.L. is grateful to ICREA Academia program.The electro-oxidation of methanol to formate is an interesting example of the potential use of renewable energies to add value to a biosourced chemical commodity. Additionally, methanol electro-oxidation can replace the sluggish oxygen evolution reaction when coupled to hydrogen evolution or to the electroreduction of other biomass-derived intermediates. But the cost-effective realization of these reaction schemes requires the development of efficient and low-cost electrocatalysts. Here, a noble metal-free catalyst, Ni FeSe nanorods, with a high potential for an efficient and selective methanol conversion to formate is demonstrated. At its optimum composition, NiFeSe, this diselenide is able to produce 0.47 mmol cm h of formate at 50 mA cm with a Faradaic conversion efficiency of 99%. Additionally, this noble-metal-free catalyst is able to continuously work for over 50 000 s with a minimal loss of efficiency, delivering initial current densities above 50 mA cm and 2.2 A mg in a 1.0 m KOH electrolyte with 1.0 m methanol at 1.5 V versus reversible hydrogen electrode. This work demonstrates the highly efficient and selective methanol-to-formate conversion on Ni-based noble-metal-free catalysts, and more importantly it shows a very promising example to exploit the electrocatalytic conversion of biomass-derived chemicals

Electron Paramagnetic Resonance Tracks Condition-Sensitive Water Radical Cation

Oxidizing species or radicals generated in water are of vital importance in catalysis, the environment, and biology. In addition to several related reactive oxygen species, using electron paramagnetic resonance (EPR), we present a nontrapping chemical transformation pathway to track water radical cation (H2O+•) species, whose formation is very sensitive to the conditioning environments, such as light irradiation, mechanical action, and gas/chemical introduction. We reveal that H2O+• can oxidize the 5,5-dimethyl-1-pyrroline N-oxide (DMPO) to the crucial epoxy hydroxylamine (HDMP=O) intermediate, which further reacts with the hydroxyl radical (•OH) for the formation of the EPR-active sextet radical (DMPO=O•). Interestingly, we uncover that H2O+• can react with dimethyl methylphosphonate (DMMP), 2-methyl-2-nitrosopropane (MNP), 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide (BMPO), and α-phenyl-N-tert-butylnitrone (PBN) which contain a double-bond structure to produce corresponding derivatives as well. It is thus expected that both H2O+• and •OH are ubiquitous in nature and in various water-containing experimental systems. These findings provide a novel perspective on radicals for water redox chemistry

A self-healing catalyst for electrocatalytic and photoelectrochemical oxygen evolution in highly alkaline conditions.

While self-healing is considered a promising strategy to achieve long-term stability for oxygen evolution reaction (OER) catalysts, this strategy remains a challenge for OER catalysts working in highly alkaline conditions. The self-healing of the OER-active nickel iron layered double hydroxides (NiFe-LDH) has not been successful due to irreversible leaching of Fe catalytic centers. Here, we investigate the introduction of cobalt (Co) into the NiFe-LDH as a promoter for in situ Fe redeposition. An active borate-intercalated NiCoFe-LDH catalyst is synthesized using electrodeposition and shows no degradation after OER tests at 10 mA cm-2 at pH 14 for 1000 h, demonstrating its self-healing ability under harsh OER conditions. Importantly, the presence of both ferrous ions and borate ions in the electrolyte is found to be crucial to the catalyst's self-healing. Furthermore, the implementation of this catalyst in photoelectrochemical devices is demonstrated with an integrated silicon photoanode. The self-healing mechanism leads to a self-limiting catalyst thickness, which is ideal for integration with photoelectrodes since redeposition is not accompanied by increased parasitic light absorption