Dynamic Potential-Ph Diagrams Application to Electrocatalysts for Water Oxidation

The construction and use of "dynamic potential-pH diagrams" (DPPDs), that are intended to extend the usefulness of thermodynamic Pourbaix diagrams to include kinetic considerations is described. As an example, DPPDs are presented for the comparison of electrocatalysts for water oxidation, i.e., the oxygen evolution reaction (OER), an important electrochemical reaction because of its key role in energy conversion devices and biological systems (water electrolyses, photoelectrochemical water splitting, plant photosynthesis). The criteria for obtaining kinetic data are discussed and a 3-D diagram, which shows the heterogeneous electron transfer kinetics of an electrochemical system as a function of pH and applied potential is presented. DPPDs are given for four catalysts: IrO(2), Co(3)O(4), Co(3)O(4) electrodeposited in a phosphate medium (Co-Pi) and Pt, allowing a direct comparison of the activity of different electrode materials over a broad range of experimental conditions (pH, potential, current density). In addition, the experimental setup and the factors affecting the accurate collection and presentation of data (e. g., reference electrode system, correction of ohmic drops, bubble formation) are discussed.Ministry of Education, University and Research PRIN 2008PF9TWZ, 2008N7CYL5Universita degli Studi di MilanoNational Science Foundation CHE-0808927Robert A. Welch Foundation F-0021Center for Electrochemistr

Promoting H2O2 production via 2-electron oxygen reduction by coordinating partially oxidized Pd with defect carbon.

Electrochemical synthesis of H2O2 through a selective two-electron (2e-) oxygen reduction reaction (ORR) is an attractive alternative to the industrial anthraquinone oxidation method, as it allows decentralized H2O2 production. Herein, we report that the synergistic interaction between partially oxidized palladium (Pdδ+) and oxygen-functionalized carbon can promote 2e- ORR in acidic electrolytes. An electrocatalyst synthesized by solution deposition of amorphous Pdδ+ clusters (Pd3δ+ and Pd4δ+) onto mildly oxidized carbon nanotubes (Pdδ+-OCNT) shows nearly 100% selectivity toward H2O2 and a positive shift of ORR onset potential by ~320 mV compared with the OCNT substrate. A high mass activity (1.946 A mg-1 at 0.45 V) of Pdδ+-OCNT is achieved. Extended X-ray absorption fine structure characterization and density functional theory calculations suggest that the interaction between Pd clusters and the nearby oxygen-containing functional groups is key for the high selectivity and activity for 2e- ORR

Elucidation of role of graphene in catalytic designs for electroreduction of oxygen

Graphene is, in principle, a promising material for consideration as component (support, active site) of electrocatalytic materials, particularly with respect to reduction of oxygen, an electrode reaction of importance to low-temperature fuel cell technology. Different concepts of utilization, including nanostructuring, doping, admixing, preconditioning, modification or functionalization of various graphene-based systems for catalytic electroreduction of oxygen are elucidated, as well as important strategies to enhance the systems' overall activity and stability are discussed

Macrocyclic cyanocobalamin (vitamin B12) as a homogeneous electrocatalyst for water oxidation under neutral conditions

Highly water-soluble cyanocobalamin (also known as vitamin B-12) is the most structurally macrocyclic complex comprising cobalt in the center of a corrin ring. Interestingly, it acts as a robust electrocatalyst in water oxidation at similar to 0.58 V overpotential with a faradaic efficiency of 97.50% under neutral buffered conditions. The catalyst is impressively stable even after long-term bulk electrolysis, and homogeneous in nature, as established by a series of experiments and characterization techniques

Steel-Based Electrocatalysts for Efficient and Durable Oxygen Evolution in Acidic Media

High overpotentials, particularly an issue of common anode materials, hamper the process of water electrolysis for clean energy generation. Thanks to immense research efforts up to date oxygen evolution electrocatalysts based on earth-abundant elements work efficiently and stably in neutral and alkaline regimes. However, non-noble metal-based anode materials that can withstand low pH regimes are considered to be an indispensable prerequisite for the water splitting to succeed in the future. All oxygen evolving electrodes working durably and actively in acids contain Ir at least as an additive. Due to its scarcity and high acquisition costs noble elements like Pt, Ru and Ir need to be replaced by earth abundant elements. We have evaluated a Ni containing stainless steel for use as an oxygen-forming electrode in diluted H2SO4. Unmodified Ni42 steel showed a significant weight loss after long term OER polarization experiments. Moreover, a substantial loss of the OER performance of the untreated steel specimen seen in linear sweep voltammetry measurements turned out to be a serious issue. However, upon anodization in LiOH, Ni42 alloy was rendered in OER electrocatalysts that exhibit under optimized synthesis conditions stable overpotentials down to 445 mV for 10 mA cm-2 current density at pH 0. Even more important: The resulting material has proven to be robust upon long-term usage (weight loss: 20 mug/mm2 after 50 ks of chronopotentiometry at pH 1) towards OER in H2SO4. Our results suggest that electrochemical oxidation of Ni42 steel in LiOH (sample Ni42Li205) results in the formation of a metal oxide containing outer zone that supports solution route-based oxygen evolution in acidic regime accompanied by a good stability of the catalyst.Comment: arXiv admin note: text overlap with arXiv:1712.0110

A critical review on sustainable biochar system through gasification: energy and environmental applications

This review lays great emphasis on production and characteristics of biochar through gasification. Specifically, the physicochemical properties and yield of biochar through the diverse gasification conditions associated with various types of biomass were extensively evaluated. In addition, potential application scenarios of biochar through gasification were explored and their environmental implications were discussed. To qualitatively evaluate biochar sustainability through the gasification process, all gasification products (i.e., syngas and biochar) were evaluated via life cycle assessment (LCA). A concept of balancing syngas and biochar production for an economically and environmentally feasible gasification system was proposed and relevant challenges and solutions were suggested in this review