A fundamental change has been achieved in understanding surface electrochemistry due to the profound knowledge of the nature of electrocatalytic processes accumulated over the past several decades and to the recent technological advances in spectroscopy and high resolution imaging. Nowadays one can preferably design electrocatalysts based on the deep theoretical knowledge of electronic structures, via computer-guided engineering of the surface and (electro)chemical properties of materials, followed by the synthesis of practical materials with high performance for specific reactions. This review provides insights into both theoretical and experimental electrochemistry toward a better understanding of a series of key clean energy conversion reactions including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The emphasis of this review is on the origin of the electrocatalytic activity of nanostructured catalysts toward the aforementioned reactions by correlating the apparent electrode performance with their intrinsic electrochemical properties. Also, a rational design of electrocatalysts is proposed starting from the most fundamental aspects of the electronic structure engineering to a more practical level of nanotechnological fabrication.

Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions

With the approaching commercialization of PEM fuel cell technology, developing active, inexpensive non-precious metal ORR catalyst materials to replace currently used Pt-based catalysts is a necessary and essential requirement in order to reduce the overall system cost. This review paper highlights the progress made over the past 40 years with a detailed discussion of recent works in the area of non-precious metal electrocatalysts for oxygen reduction reaction, a necessary reaction at the PEM fuel cell cathode. Several important kinds of unsupported or carbon supported non-precious metal electrocatalysts for ORR are reviewed, including non-pyrolyzed and pyrolyzed transition metal nitrogen-containing complexes, conductive polymer-based catalysts, transition metal chalcogenides, metal oxides/carbides/nitrides/oxynitrides/carbonitrides, and enzymatic compounds. Among these candidates, pyrolyzed transition metal nitrogen-containing complexes supported on carbon materials (M–Nx/C) are considered the most promising ORR catalysts because they have demonstrated some ORR activity and stability close to that of commercially available Pt/C catalysts. Although great progress has been achieved in this area of research and development, there are still some challenges in both their ORR activity and stability. Regarding the ORR activity, the actual volumetric activity of the most active non-precious metal catalyst is still well below the DOE 2015 target. Regarding the ORR stability, stability tests are generally run at low current densities or low power levels, and the lifetime is far shorter than targets set by DOE. Therefore, improving both the ORR activity and stability are the major short and long term focuses of non-precious metal catalyst research and development. Based on the results achieved in this area, several future research directions are also proposed and discussed in this paper.

A review on non-precious metal electrocatalysts for PEM fuel cells

Electrochemical energy storage systems (batteries) have a tremendous role in technical applications In this review the authors examine the prospects of electroactive polymers in view of the properties required for such batteries Conducting organic polymers are considered here in the light of their rugged chemical environment: organic solvents, acids, and alkalis The goal of the present article is to provide, first of all in tabular form, a survey of electroactive polymers in view of potential applications in rechargeable batteries It reviews the preparative methods and the electrochemical performance of polymers as rechargeable battery electrodes The theoretical values of specific charge of the polymers are comparable to those of metal oxide electrodes, but are not as high as those of most of the metal electrodes normally used in batteries Therefore, it is an advantage in conventional battery designs to use the conducting polymer as a positive electrode material in combination with a negative electrode such as Li, Na, Mg, Zn, MeH{sub x}, etc 504 refs

Electrochemically Active Polymers for Rechargeable Batteries.

Understanding the origin of high activity of Fe–N–C electrocatalysts in oxygen reduction reaction (ORR) is critical but still challenging for developing efficient sustainable nonprecious metal catalysts in fuel cells and metal–air batteries. Herein, we developed a new highly active Fe–N–C ORR catalyst containing Fe–Nx coordination sites and Fe/Fe3C nanocrystals (Fe@C-FeNC), and revealed the origin of its activity by intensively investigating the composition and the structure of the catalyst and their correlations with the electrochemical performance. The detailed analyses unambiguously confirmed the coexistence of Fe/Fe3C nanocrystals and Fe–Nx in the best catalyst. A series of designed experiments disclosed that (1) N-doped carbon substrate, Fe/Fe3C nanocrystals or Fe–Nx themselves did not deliver the high activity; (2) the catalysts with both Fe/Fe3C nanocrystals and Fe–Nx exhibited the high activity; (3) the higher content of Fe–Nx gave the higher activity; (4) the removal of Fe/Fe3C nanocrystals sever...

Understanding the High Activity of Fe-N-C Electrocatalysts in Oxygen Reduction: Fe/Fe3C Nanoparticles Boost the Activity of Fe-N(x).

Despite the dedicated search for novel catalysts for fuel cell applications, the intrinsic oxygen reduction reaction (ORR) activity of materials has not improved significantly over the past decade. Here, we review the role of theory in understanding the ORR mechanism and highlight the descriptor-based approaches that have been used to identify catalysts with increased activity. Specifically, by showing that the performance of the commonly studied materials (e.g., metals, alloys, carbons, etc.) is limited by unfavorable scaling relationships (for binding energies of reaction intermediates), we present a number of alternative strategies that may lead to the design and discovery of more promising materials for ORR.

Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction.

Metallophthalocyanines as catalysts in electrochemical reactions

Metallophthalocyanine-based molecular materials as catalysts for electrochemical reactions

Similarities are established between well-known reactivity descriptors of metal electrodes for their activity in the oxygen reduction reaction (ORR) and the reactivity of molecular catalysts, in particular macrocyclic MN4 metal complexes confined to electrode surfaces. We show that there is a correlation between the MIII /MII redox potential of MN4 chelates and the M-O2 binding energies. Specifically, the binding energy of O2 (and other O species) follows the MIII -OH/MII redox transition for MnN4 and FeN4 chelates. The ORR volcano plot for MN4 catalysts is similar to that for metal catalysts: catalysts on the weak binding side (mostly CoN4 chelates) yield mainly H2 O2 as the product, with an ORR onset potential independent of the pH value on the NHE scale (and therefore pH-dependent on the RHE scale); catalysts on the stronger binding side yield H2 O as the product with the expected pH-dependence on the NHE scale. The suggested descriptors also apply to heat-treated pyrolyzed MN4 catalysts.

Reactivity Descriptors for the Activity of Molecular MN4 Catalysts for the Oxygen Reduction Reaction.

Billion-Year-Old Oxygen Cathode that Actually Works: Respiratory Oxygen Reduction and Its Biomimetic Analogs.- Fundamental Aspects on the Catalytic Activity of Metallomacrocyclics for the Electrochemical Reduction of O2.- Oxygen Reduction in PEM Fuel Cell Conditions: Heat-Treated Non-Precious Metal-N4 Macrocycles and Beyond.- Biomimetic NOx Reductions by Heme Models and Proteins.- Electroreduction of CO2 Catalyzed by Metallomacrocyclics.- Supramolecular Porphyrins as Electrocatalysts.- Electrodes Modified with Monomeric M-N4 Catalysts for the Detection of Environmentally Important Molecules.- Electropolymerized Metalloporphyrin Metallophthalocyanine and Metal Schiff Base Complex Films: Applications to Biomimetic Electrocatalysis and Bioelectroanalysis.- Electron Transfer Processes of ?-Pyrrole Brominated Porphyrins: Structural vs. Electronic Effects.- Photoelectrochemical Reactions at Phthalocyanine Electrodes.- Organisation and Photoelectrochemical Reactivity of Water-Soluble Metalloporphyrins at the Liquid/Liquid Interface.- Theoretical Insights on the Chemical Reactivity of Metalloporphyrins Using Density Functional Theory.- Organized Multiporphyrinic Assemblies for Photoconduction and Electroconduction.- Vibrational Spectra and Surface-Enhanced Vibrational Spectra of Azamacrocycles.

José H. Zagal

Papers

Metallophthalocyanines as catalysts in electrochemical reactions

Metallophthalocyanine-based molecular materials as catalysts for electrochemical reactions

Reactivity Descriptors for the Activity of Molecular MN4 Catalysts for the Oxygen Reduction Reaction.

N4-Macrocyclic Metal Complexes

Electrocatalytic activity of metal phthalocyanines for oxygen reduction