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The electron-transfer process during the oxygen evolution reaction (OER) often either proceeds solely via a metal redox chemistry (adsorbate evolution mechanism (AEM), with metal bands around the Fermi level) or an oxygen redox chemistry (lattice oxygen oxidation mechanism (LOM), with oxygen bands around the Fermi level). Unlike the AEM, the LOM involves oxygen redox chemistry instead of metal redox, which leads to the formation of a direct oxygen-oxygen (OO) bond. As a result, such a process is able to bypass the rate-determining step, that is, OO bonding, in AEM, which highlights the critical advantage of LOM as compared to the conventional AEM. Thus, it has been well reported that LOM-based catalysts are able to demonstrate higher OER activities as compared to AEM-based catalysts. Here, a comprehensive understanding of the oxygen redox in LOM and all documented and possible characterization techniques that can be used to identify the oxygen redox are reviewed. This review will interpret the origins of oxygen redox in the reported LOM-based electrocatalysts and the underlying science of LOM-induced surface reconstruction in transition metal oxides. Finally, perspectives on the future development of LOM electrocatalysts are also provided.

Defect-engineered perovskite oxides that exhibit ferroelectric and photovoltaic properties are promising multifunctional materials. Though introducing gap states by transition metal doping on the perovskite B-site can obtain low bandgap (i.e., 1.1-3.8 eV), the electrically leaky perovskite oxides generally lose piezoelectricity mainly due to oxygen vacancies. Therefore, the development of highly piezoelectric ferroelectric semiconductor remains challenging. Here, inspired by point-defect-mediated large piezoelectricity in ferroelectrics especially at the morphotropic phase boundary (MPB) region, an efficient strategy is proposed by judiciously introducing the gap states at the MPB where defect-induced local polar heterogeneities are thermodynamically coupled with the host polarization to simultaneously achieve high piezoelectricity and low bandgap. A concrete example, Ni2+ -mediated (1-x)Na0.5 Bi0.5 TiO3 -xBa(Ti0.5 Ni0.5 )O3-δ (x = 0.02-0.08) composition is presented, which can show excellent piezoelectricity and unprecedented visible/near-infrared light absorption with a lowest ever bandgap ≈0.9 eV at room temperature. In particular, the MPB composition x = 0.05 shows the best ferroelectricity/piezoelectricity (d33 = 151 pC N-1 , Pr = 31.2 μC cm-2 ) and a largely enhanced photocurrent density approximately two orders of magnitude higher compared with classic ferroelectric (Pb,La)(Zr,Ti)O3 . This research provides a new paradigm for designing highly piezoelectric and visible/near-infrared photoresponsive perovskite oxides for solar energy conversion, near-infrared detection, and other multifunctional applications.