The oxygen reduction reaction (ORR) is a key reaction for energy conversion and storage systems such as polymer electrolyte membrane fuel cells (PEMFCs). Studies on Pt and Pt-transition metal alloy single crystals have established that the ORR is best electrocatalyzed on bimetallic alloys and at (111) facets. Combining alloying and ensemble effects recently led to 20-30-fold enhancement of the specific activity (normalized per real cm 2 of catalyst) for the ORR on PtNi/C nanooctahedra relative to Pt/C nanoparticles. However, due to the highly oxidizing conditions of the PEMFC cathode, the stability of PtNi/C octahedra is poor in PEMFC cathode operating conditions, thus compromising their utilization in real devices. Strikingly, it also turned out recently that structurally-disordered PtNi nano-catalysts, such as hollow PtNi/C nanoparticles, dealloyed PtNi/C nanoparticles, PtNi aerogels or PtNi nanowires feature highly desirable and sustainable ORR activity (x 10-12 in specific activity relative to pure Pt/C). However, to date, the mechanisms of this unexpected ORR activity enhancement remain unclear, and prevent further development of this vital technology for a carbon-free energy future. To shed fundamental light onto these issues, state-of-the art PtNi/C nanocatalysts with distinct atomic composition, size, shape and density of disorder were synthesized. Their disorder was quantified experimentally, using the values of microstrain (a parameter accessible by the Rietveld refinement of wide-angle X-ray scattering patterns) that is representative of the local distortion of a crystal lattice. Thanks to ab initio calculations, the contributions of bulk and surface structural disorder were disentangled, and a new parameter, the surface distortion (SD), was established. The SD descriptor was used to rationalize the ORR activity enhancement of the two classes of materials (structurally-ordered and structurally-disordered), and to probe their stability in simulated PEMFC cathode operating conditions.

Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis

FeCo/FeCoP encapsulated in N, Mn-codoped three-dimensional fluffy porous carbon nanostructures as highly efficient bifunctional electrocatalyst with multi-components synergistic catalysis for ultra-stable rechargeable Zn-air batteries.

FeCo/FeCoP encapsulated in N, Mn-codoped three-dimensional fluffy porous carbon nanostructures as highly efficient bifunctional electrocatalyst with multi-components synergistic catalysis for ultra-stable rechargeable Zn-air batteries

Metal–nitrogen–carbon (M–N–C) materials have attracted much interest in bifunctional oxygen‐involving electrocatalysis for rechargeable Zn–air batteries. Such M–N–C electrocatalysts with M–Nx sites show good activity for the oxygen reduction reaction (ORR) but moderate activity for the oxygen evolution reaction (OER). Herein, an oxygen‐rich M–N–C material (O–Co–N/C) with a highly porous nanosheet structure is reported as a bifunctional oxygen electrocatalyst, which is prepared by the direct pyrolysis of ultrathin CoO nanosheets decorated with zeolitic imidazolate framework‐8 nanoparticles under an inert atmosphere. Particularly, Co nanoparticles in the O–Co–N/C electrocatalyst contain both Co–Nx and Co–Ox coordination environments to provide intrinsic active sites for the ORR and OER, respectively. Furthermore, electrochemical studies show that the O–Co–N/C catalyst retains comparable ORR activity to common M–N–C materials with a half‐wave potential of 0.85 V vs the reversible hydrogen electrode and better OER activity with an overpotential of 0.29 V at the current density of 10 mA cm−2. This study provides insights into the development of effective oxygen‐involving electrocatalysts with bifunctional metal active centers coordinated by both nitrogen and oxygen atoms.

Oxygen‐Rich Cobalt–Nitrogen–Carbon Porous Nanosheets for Bifunctional Oxygen Electrocatalysis

https://onlinelibrary.wiley.com/doi/pdf/10.1002/smsc.202100044

Recent Advances in Electrode Design for Rechargeable Zinc–Air Batteries

Developing a highly efficient, easy-to-fabricate and non-noble metal electrocatalyst is vital for the oxygen reduction reaction (ORR). Herein, we fabricate a single Fe site catalyst Fe1/d-CN by developing a double-layer MOF strategy. The Fe1/d-CN catalyst shows an excellent ORR activity in the pH-universal range, especially in alkaline electrolytes with a record-level half-wave potential of 0.950 V, exceeding those of almost all the reported non-noble electrocatalysts and the commercial Pt/C catalyst (0.863 V). Besides its exceptional ORR activity in alkaline electrolytes, it also exhibits comparable ORR activity to the commercial Pt/C catalyst in acidic and neutral electrolytes. We speculate that the sources of the excellent pH-universal ORR performance can be attributed to the regulation of the electronic structure of Fe centres and the excellent electron/proton transport capability that comes from the rich defects and hierarchical porous features of the Fe1/d-CN catalyst. More excitingly, the catalyst possesses remarkable durability, and exhibits a negligible decrease after 30k accelerated durability test (ADT) cycles in pH-universal media. The flexible quasi-solid-state alkaline rechargeable Zn–air batteries with the Fe1/d-CN catalyst as the cathode show superior performance such as a high OCV of 1.50 V and peak power density of 78.0 mW cm−2. Furthermore, the flexible quasi-solid-state neutral rechargeable Zn–air batteries also exhibited remarkable performance.

A pH-universal ORR catalyst with single-atom iron sites derived from a double-layer MOF for superior flexible quasi-solid-state rechargeable Zn–air batteries

The rechargeable Zn-air batteries as an environmentally friendly sustainable energy technology have been extensively studied. However, it is still a challenge to develop non-noble metal bifunctional catalysts with high oxygen reduction as well as oxygen evolution reaction (ORR and OER) activity and superior durability, which limit the large-scale application of rechargeable Zn-air batteries. Herein, we synthesized an ultrastable FeCo bifunctional oxygen electrocatalyst on Se-doped CNTs (FeCo/Se-CNT) via a gravity guided chemical vapor deposition (CVD) strategy. The catalyst exhibits excellent ORR (E1/2 = 0.9 V) and OER (overpotential at 10 mA cm-2 = 340 mV) properties simultaneously, surpassing commercial Pt/C and RuO2/C catalysts. More importantly, the catalyst shows an unordinary stability, that is, is no obvious decrease after 30K cycles accelerated durability test for ORR and OER processes. The small potential gap (0.75 V) represents superior bifunctional ORR and OER activities of the FeCo/Se-CNT catalyst. The FeCo/Se-CNT catalyst possesses outstanding electrochemical performance for the rechargeable liquid and flexible all-solid-state Zn-air batteries, for example, a high open circuit voltage (OCV) and peak power density of 1.543 and 1.405 V and 173.4 and 37.5 mW cm-2, respectively.

Hongwei Zhang

Papers

A pH-universal ORR catalyst with single-atom iron sites derived from a double-layer MOF for superior flexible quasi-solid-state rechargeable Zn–air batteries

Ultrastable FeCo Bifunctional Electrocatalyst on Se-Doped CNTs for Liquid and Flexible All-Solid-State Rechargeable Zn-Air Batteries.

Electron-rich isolated Pt active sites in ultrafine PtFe3 intermetallic catalyst for efficient alkene hydrosilylation