There is still an ongoing effort to search for sustainable, clean and highly efficient energy generation to satisfy the energy needs of modern society. Among various advanced technologies, electrocatalysis for the oxygen evolution reaction (OER) plays a key role and numerous new electrocatalysts have been developed to improve the efficiency of gas evolution. Along the way, enormous effort has been devoted to finding high-performance electrocatalysts, which has also stimulated the invention of new techniques to investigate the properties of materials or the fundamental mechanism of the OER. This accumulated knowledge not only establishes the foundation of the mechanism of the OER, but also points out the important criteria for a good electrocatalyst based on a variety of studies. Even though it may be difficult to include all cases, the aim of this review is to inspect the current progress and offer a comprehensive insight toward the OER. This review begins with examining the theoretical principles of electrode kinetics and some measurement criteria for achieving a fair evaluation among the catalysts. The second part of this review acquaints some materials for performing OER activity, in which the metal oxide materials build the basis of OER mechanism while non-oxide materials exhibit greatly promising performance toward overall water-splitting. Attention of this review is also paid to in situ approaches to electrocatalytic behavior during OER, and this information is crucial and can provide efficient strategies to design perfect electrocatalysts for OER. Finally, the OER mechanism from the perspective of both recent experimental and theoretical investigations is discussed, as well as probable strategies for improving OER performance with regards to future developments.

Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives

Over the past few decades, researchers have established artificial enzymes as highly stable and low-cost alternatives to natural enzymes in a wide range of applications. A variety of materials including cyclodextrins, metal complexes, porphyrins, polymers, dendrimers and biomolecules have been extensively explored to mimic the structures and functions of naturally occurring enzymes. Recently, some nanomaterials have been found to exhibit unexpected enzyme-like activities, and great advances have been made in this area due to the tremendous progress in nano-research and the unique characteristics of nanomaterials. To highlight the progress in the field of nanomaterial-based artificial enzymes (nanozymes), this review discusses various nanomaterials that have been explored to mimic different kinds of enzymes. We cover their kinetics, mechanisms and applications in numerous fields, from biosensing and immunoassays, to stem cell growth and pollutant removal. We also summarize several approaches to tune the activities of nanozymes. Finally, we make comparisons between nanozymes and other catalytic materials (other artificial enzymes, natural enzymes, organic catalysts and nanomaterial-based catalysts) and address the current challenges and future directions (302 references).

Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes

High-performance gas sensors prepared using p-type oxide semiconductors such as NiO, CuO, Cr2O3, Co3O4, and Mn3O4 were reviewed. The ionized adsorption of oxygen on p-type oxide semiconductors leads to the formation of hole-accumulation layers (HALs), and conduction occurs mainly along the near-surface HAL. Thus, the chemoresistive variations of undoped p-type oxide semiconductors are lower than those induced at the electron-depletion layers of n-type oxide semiconductors. However, highly sensitive and selective p-type oxide-semiconductor-based gas sensors can be designed either by controlling the carrier concentration through aliovalent doping or by promoting the sensing reaction of a specific gas through doping/loading the sensor material with oxide or noble metal catalysts. The junction between p- and n-type oxide semiconductors fabricated with different contact configurations can provide new strategies for designing gas sensors. p-Type oxide semiconductors with distinctive surface reactivity and oxygen adsorption are also advantageous for enhancing gas selectivity, decreasing the humidity dependence of sensor signals to negligible levels, and improving recovery speed. Accordingly, p-type oxide semiconductors are excellent materials not only for fabricating highly sensitive and selective gas sensors but also valuable additives that provide new functionality in gas sensors, which will enable the development of high-performance gas sensors.

Highly sensitive and selective gas sensors using p-type oxide semiconductors: Overview

Persistent organic pollutants (POPs) are carbon-based chemical substances that are resistant to environmental degradation and may not be completely removed through treatment processes. Their persistence can contribute to adverse health impacts on wild-life and human beings. Thus, the solar photocatalysis process has received increasing attention due to its great potential as a green and eco-friendly process for the elimination of POPs to increase the security of clean water. In this context, ZnO nanostructures have been shown to be prominent photocatalyst candidates to be used in photodegradation owing to the facts that they are low-cost, non-toxic and more efficient in the absorption across a large fraction of the solar spectrum compared to TiO 2 . There are several aspects, however, need to be taken into consideration for further development. The purpose of this paper is to review the photo-degradation mechanisms of POPs and the recent progress in ZnO nanostructured fabrication methods including doping, heterojunction and modification techniques as well as improvements of ZnO as a photocatalyst. The second objective of this review is to evaluate the immobilization of photocatalyst and suspension systems while looking into their future challenges and prospects.

A review of ZnO nanoparticles as solar photocatalysts: Synthesis, mechanisms and applications

Metal oxide-based resistive-type gas sensors are solid-state devices which are widely used in a number of applications from health and safety to energy efficiency and emission control. Nanomaterials such as nanowires, nanorods, and nanoparticles have dominated the research focus in this field due to their large number of surface sites facilitating surface reactions. Previous studies have shown that incorporating two or more metal oxides to form a heterojunction interface can have drastic effects on gas sensor performance, especially the selectivity. Recently, these effects have been amplified by designing heterojunctions on the nano-scale. These designs have evolved from mixed commercial powders and bi-layer films to finely-tuned core–shell and hierarchical brush-like nanocomposites. This review details the various morphological classes currently available for nanostructured metal-oxide based heterojunctions and then presents the dominant electronic and chemical mechanisms that influence the performance of these materials as resistive-type gas sensors. Mechanisms explored include p–n and n–n potential barrier manipulation, n–p–n response type inversions, spill-over effects, synergistic catalytic behavior, and microstructure enhancement. Tables are presented summarizing these works specifically for SnO2, ZnO, TiO2, In2O3, Fe2O3, MoO3, Co3O4, and CdO-based nanocomposites. Recent developments are highlighted and likely future trends are explored.

Nanoscale metal oxide-based heterojunctions for gas sensing: A review

Cobalt sulfide materials have attracted enormous interest as low-cost alternatives to noble-metal catalysts capable of catalyzing both oxygen reduction and oxygen evolution reactions. Although recent advances have been achieved in the development of various cobalt sulfide composites to expedite their oxygen reduction reaction properties, to improve their poor oxygen evolution reaction (OER) activity is still challenging, which significantly limits their utilization. Here, the synthesis of Fe3O4-decorated Co9S8 nanoparticles in situ grown on a reduced graphene oxide surface (Fe3O4@Co9S8/rGO) and the use of it as a remarkably active and stable OER catalyst are first reported. Loading of Fe3O4 on cobalt sulfide induces the formation of pure phase Co9S8 and highly improves the catalytic activity for OER. The composite exhibits superior OER performance with a small overpotential of 0.34 V at the current density of 10 mA cm−2 and high stability. It is believed that the electron transfer trend from Fe species to Co9S8 promotes the breaking of the Co–O bond in the stable configuration (Co–O–O superoxo group), attributing to the excellent catalytic activity. This development offers a new and effective cobalt sulfide-based oxygen evolution electrocatalysts to replace the expensive commercial catalysts such as RuO2 or IrO2.

Fe3O4‐Decorated Co9S8 Nanoparticles In Situ Grown on Reduced Graphene Oxide: A New and Efficient Electrocatalyst for Oxygen Evolution Reaction

Hierarchically porous CuO architectures were successfully fabricated via copper basic carbonate precursor obtained with a facile hydrothermal route. The shape of the precursor is preserved after its conversion to porous CuO architectures by calcination. The obtained CuO are systemically characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller N2 adsorption–desorption analysis. The results reveal that hierarchical CuO microspheres are monoclinic structure and are assembled by porous single-crystal sub-microplatelets. The Brunauer–Emmett–Teller N2 adsorption–desorption analysis indicates that the obtained CuO has a surface area of 12.0 m2/g with pore size of around 30 nm. The gas sensing performance of the as-prepared hierarchical CuO microspheres were investigated towards a series of typical organic solvents and fuels. They exhibit higher sensing response than that of commercial CuO powder. Their sensing properties can be further ...

Facile Fabrication and Enhanced Sensing Properties of Hierarchically Porous CuO Architectures

A facile and robust route for the mass preparation of hollow NiO microspheres assembled from nanosheet-stacked nanoparticles is developed. The Ni(HCO3)2 precursor with a hollow spherical structure was firstly prepared by a hydrothermal reaction without any surfactants or organic additives. The reaction generated gas bubble may act as a template for the formation of Ni(HCO3)2 hollow microspheres. These are converted into hierarchical NiO hollow microspheres assembled from nanoparticles (with diameter of ∼25 nm) upon calcination, which are further assembled by the stacking of ultrathin nanosheets. The hierarchical NiO hollow structures are attractive for catalyst, sensor and environmental applications, benefiting from their large surfaces. The sensing properties of the hierarchical NiO hollow microspheres were evaluated. They show high sensitivity, short response and recovery times, and good response and recovery characteristics to n-butanol. As compared with NiO nanoparticles with similar dimensions (∼20–35 nm), the nanoparticle assembled NiO hollow microspheres exhibit enhanced gas sensing properties. The effective integration of several nanostructures in one microunit would provide a novel way to design new materials for nanodevices.

Hierarchical NiO hollow microspheres assembled from nanosheet-stacked nanoparticles and their application in a gas sensor

FeCo-based materials are promising candidates as efficient, affordable, and sustainable electrocatalysts for oxygen evolution reaction (OER). Herein, a composite based on FeSe2@CoSe2 particles supported on reduced graphene oxide (rGO) was successfully prepared as an OER catalyst. In the catalyst, the CoSe2 phase was located on the FeSe2 surface, forming a large number of exposed heterointerfaces with acidic iron sites because of strong charge interaction between CoSe2 and FeSe2. It is believed that the exposed heterointerfaces act as catalytic active sites for OER via a two-site mechanism, manifesting an overpotential as low as 260 mV to reach the current density of 10 mA cm–2 in 1 M KOH and excellent stability for at least 6 h, which is superior to those of CoSe2/rGO, FeSe2/rGO, as well as most of the FeNi- and FeCo-based electrocatalysts reported in recent literatures. It was demonstrated that the most optimal composite electrocatalysts release more Fe species into the electrolyte during the OER process...

Nanocomposites Based on CoSe2-Decorated FeSe2 Nanoparticles Supported on Reduced Graphene Oxide as High-Performance Electrocatalysts toward Oxygen Evolution Reaction.

Co3O4 mesocrystals with concave octahedral structures were successfully prepared by a facile, polymer-mediated route. The Co3O4 mesocrystals are obtained from the oriented aggregation of primary nanocrystals from their six identical [100] directions. After a thorough investigation of their structure as a function of the adopted preparation parameters such as reaction time and the amount of polymer, the gas sensing performance of the Co3O4 mesocrystals was studied with formaldehyde and ethanol as probe analytes. It was found that they show high sensitivity and good response and recovery characteristics. As compared with Co3O4 powder, the Co3O4 mesocrystals exhibit 1.8-fold and 1.4-fold enhancement in gas responses to 100 ppm of formaldehyde and ethanol, respectively.

Yuanjun Liu

Papers

Fe3O4‐Decorated Co9S8 Nanoparticles In Situ Grown on Reduced Graphene Oxide: A New and Efficient Electrocatalyst for Oxygen Evolution Reaction

Facile Fabrication and Enhanced Sensing Properties of Hierarchically Porous CuO Architectures

Hierarchical NiO hollow microspheres assembled from nanosheet-stacked nanoparticles and their application in a gas sensor

Nanocomposites Based on CoSe2-Decorated FeSe2 Nanoparticles Supported on Reduced Graphene Oxide as High-Performance Electrocatalysts toward Oxygen Evolution Reaction.

Concave Co3O4 octahedral mesocrystal: polymer-mediated synthesis and sensing properties