Significance of Engineering the MnO6 Octahedral Units to Promote the Oxygen Reduction Reaction of Perovskite Oxides.

The electronic structure and geometric configuration of catalysts play a crucial role to design novel perovskite-type catalysts for oxygen reduction reaction (ORR). Nowadays, many studies are more concerned with the influence of electronic structure and ignore the geometric effect, which plays a nonnegligible role in enhancing catalytic performances. Herein, this work regulates the MnO6 octahedral tilting degree of LaMnO3 by modulating the concentration of Y3+, excluding the electronic effect from the valence state of manganese. Plotting the MnO6 octahedral tilting degree as a function of concentration of Y3+ produces a volcano-shaped plot. The octahedral tilting can reduce the Mn-O covalency, generating more highly active Mn3+ and oxygen vacancies during ORR process. The specific activity has a positive correlation with octahedral tilting degree. Meanwhile, the octahedral tilting stabilizes Mn-O interactions during ORR process and promote stability. Based on experimental results and DFT calculations, octahedral tilting alters the rate-determining step (RDS) and decrease the energy barrier. Subsequent extended experiment confirms that octahedral tilting is the key factor to affect the catalytic performances.

Triggered lattice-oxygen oxidation with active-site generation and self-termination of surface reconstruction during water oxidation.

To master the activation law and mechanism of surface lattice oxygen for the oxygen evolution reaction (OER) is critical for the development of efficient water electrolysis. Herein, we propose a strategy for triggering lattice-oxygen oxidation and enabling non-concerted proton-electron transfers during OER conditions by substituting Al in La0.3Sr0.7CoO3-δ. According to our experimental data and density functional theory calculations, the substitution of Al can have a dual effect of promoting surface reconstruction into active Co oxyhydroxides and activating deprotonation on the reconstructed oxyhydroxide, inducing negatively charged oxygen as an active site. This leads to a significant improvement in the OER activity. Additionally, Al dopants facilitate the preoxidation of active cobalt metal, which introduces great structural flexibility due to elevated O 2p levels. As OER progresses, the accumulation of oxygen vacancies and lattice-oxygen oxidation on the catalyst surface leads to the termination of Al3+ leaching, thereby preventing further reconstruction. We have demonstrated a promising approach to achieving tunable electrochemical reconstruction by optimizing the electronic structure and gained a fundamental understanding of the activation mechanism of surface oxygen sites.

CeO2 Promotes CO2 Electroreduction to Formate on Bi2S3 via Tuning of the *OCHO Intermediate.

Formate is identified as economically viable chemical fuel from electrochemical carbon dioxide reduction. However, the selectivity of current catalysts toward formate is limited by the competitive reaction such as HER. Herein, we propose a CeO2 modification strategy to improve the selectivity of catalysts for formate through tuning of the *OCHO intermediate, which is important for formate production.

Synthesis of Bandgap-tunable Transition Metal Sulfides through Gas-phase Cation Exchange-induced Topological Transformation.

Oriented synthesis of transition metal sulfides (TMSs) with controlled compositions and crystal structures has long been promising for electronic devices and energy applications. Liquid-phase cation exchange (LCE) is a well-studied route by varying the compositions. However, achieving crystal structure selectivity is still a great challenge. Here, we demonstrate gas-phase cation exchange (GCE), which can induce a specific topological transformation (TT), for the synthesis of versatile TMSs with identified cubic or hexagonal crystal structures. The parallel six-sided subunit (PSS), a new descriptor, is defined to describe the substitution of cations and the transition of the anion sublattice. Under this principle, the band gap of targeted TMSs can be tailored. Using the photocatalytic hydrogen evolution as an example, the optimal hydrogen evolution rate of a zinc-cadmium sulfide (ZCS4) is determined to be 11.59 mmol h-1 g-1 , showing a 36.2-fold improvement over CdS.

Boosting the Electrocatalytic Oxygen Evolution of Perovskite LaCo1- x Fex O3 by the Construction of Yolk-Shell Nanostructures and Electronic Modulation.

Realizing the rational design of perovskite oxides with controllable compositions and nanostructures remains a tremendous challenge for the development of efficient electrocatalysts. Herein, a ligand-assisted synthetic strategy to fabricate perovskite oxides LaCo1- x Fex O3 with yolk-shell nanostructures is developed. Benefiting from the unique structural and compositional merits, LaCo0.75 Fe0.25 O3 exhibits an overpotential of 310 mV at a current density of 10 mA cm-2 and long-term stability of 100 h for the oxygen evolution reaction. In situ Raman spectroscopy demonstrates that Fe substitution facilitates the pre-oxidation of Co sites and induces the surface reconstruction into active Co oxyhydroxides at a relatively lower applied potential, guaranteeing excellent catalytic performances. Density functional theory calculations unravel that the appropriate introduction of Fe into perovskite LaCoO3 leads to the improved electroactivity and durability of the catalyst for the oxygen evolution reaction (OER). Fe-3d orbitals show a pinning effect on Co-3d orbitals to maintain the stable valence state of Co sites at the low overpotential of the OER. Furthermore, Zn-air batteries (ZABs) assembled with LaCo0.75 Fe0.25 O3 display a high open circuit potential of 1.47 V, superior energy density of 905 Wh kg-1  Zn , and excellent stability in a large temperature range. This work supplies novel insights into the future developments of perovskite-based electrocatalysts.

Controlling the Cation Exsolution of Perovskite to Customize Heterostructure Active Site for Oxygen Evolution Reaction.

Perovskite oxides are an important class of oxygen evolution reaction (OER) catalysts offering an ordered atomic arrangement and a highly flexible electronic structure. Currently, understanding and adjusting the dynamic reconstruction of perovskite during the OER process remains a formidable challenge. Here, we report the artificial construction of a heterostructure by the cation exsolution of perovskite to control the active site formation and reconstruction. The deliberately made La deficiency in LaNiO3 perovskite facilitates the original segregation of NiO from the parent matrix and forms a well-defined interface between perovskite parent and NiO exsolution phase. The dynamic formation process of such heterojunction was studied by density functional theory computation and high quality imaging characterization. Due to the valence redistribution of Ni ions caused by the interfacial electron transfer, the in situ formed LaNiO3/NiO heterostructure displays high electroactivity. Therefore, the LaNiO3/NiO heterostructure exhibits a dynamic surface evolution feature with the generation of the highly active NiOOH layer under a low anodic potential (∼1.35 V vs RHE) during the OER process, which is very different from the conventional LaNiO3 with a stoichiometry and NiO catalysts. With the newly formed heterostructure, the reconstructed catalysts impart a 4.5-fold increase in OER activity and a 3-fold improvement in stability against La and Ni dissolution during the OER process. This work provides a feasible interface engineering strategy for artificially controlling the reconstruction of the active phase in high-performance perovskite-based electrocatalytic materials.

Activation Strategies of Perovskite-Type Structure for Applications in Oxygen-Related Electrocatalysts.

The oxygen-related electrochemical process, including the oxygen evolution reaction and oxygen reduction reaction, is usually a kinetically sluggish reaction and thus dominates the whole efficiency of energy storage and conversion devices. Owing to the dominant role of the oxygen-related electrochemical process in the development of electrochemical energy, an abundance of oxygen-related electrocatalysts is discovered. Among them, perovskite-type materials with flexible crystal and electronic structures have been researched for a long time. However, most perovskite materials still show low intrinsic activity, which highlights the importance of activation strategies for perovskite-type structures to improve their intrinsic activity. In this review, the recent progress of the activation strategies for perovskite-type structures is summarized and their related applications in oxygen-related electrocatalysis reactions, including electrochemistry water splitting, metal-air batteries, and solid oxide fuel cells are discussed. Furthermore, the existing challenges and the future perspectives for the designing of ideal perovskite-type structure catalysts are proposed and discussed.

Uncovering the Promotion of CeO2 /CoS1.97 Heterostructure with Specific Spatial Architectures on Oxygen Evolution Reaction.

Structural engineering and compositional controlling are extensively applied in rationally designing and fabricating advanced freestanding electrocatalysts. The key relationship between the spatial distribution of components and enhanced electrocatalysis performance still needs further elaborate elucidation. Here, CeO2 substrate supported CoS1.97 (CeO2 -CoS1.97 ) and CoS1.97 with CeO2 surface decorated (CoS1.97 -CeO2 ) materials are constructed to comprehensively investigate the origin of spatial architectures for the oxygen evolution reaction (OER). CeO2 -CoS1.97 exhibits a low overpotential of 264 mV at 10 mA cm-2 due to the stable heterostructure and faster mass transfer. Meanwhile, CoS1.97 -CeO2 has a smaller Tafel slope of 49 mV dec-1 through enhanced adsorption of OH- , fast electron transfer, and in situ formation of Co(IV)O2 species under the OER condition. Furthermore, operando spectroscopic characterizations combined with theoretical calculations demonstrate that spatial architectures play a distinguished role in modulating the electronic structure and promoting the reconstruction from sulfide to oxyhydroxide toward higher chemical valence. The findings highlight spatial architectures and surface reconstruction in designing advanced electrocatalytic materials.

Atomic-level structure engineering of metal oxides for high-rate oxygen intercalation pseudocapacitance.

Atomic-level structure engineering can substantially change the chemical and physical properties of materials. However, the effects of structure engineering on the capacitive properties of electrode materials at the atomic scale are poorly understood. Fast transport of ions and electrons to all active sites of electrode materials remains a grand challenge. Here, we report the radical modification of the pseudocapacitive properties of an oxide material, Zn x Co1-x O, via atomic-level structure engineering, which changes its dominant charge storage mechanism from surface redox reactions to ion intercalation into bulk material. Fast ion and electron transports are simultaneously achieved in this mixed oxide, increasing its capacity almost to the theoretical limit. The resultant Zn x Co1-x O exhibits high-rate performance with capacitance up to 450 F g-1 at a scan rate of 1 V s-1, competing with the state-of-the-art transition metal carbides. A symmetric device assembled with Zn x Co1-x O achieves an energy density of 67.3 watt-hour kg-1 at a power density of 1.67 kW kg-1, which is the highest value ever reported for symmetric pseudocapacitors. Our finding suggests that the rational design of electrode materials at the atomic scale opens a new opportunity for achieving high power/energy density electrode materials for advanced energy storage devices.

Multiscale Structural Engineering of Ni-Doped CoO Nanosheets for Zinc-Air Batteries with High Power Density.

Zinc-air batteries offer a possible solution for large-scale energy storage due to their superhigh theoretical energy density, reliable safety, low cost, and long durability. However, their widespread application is hindered by low power density. Herein, a multiscale structural engineering of Ni-doped CoO nanosheets (NSs) for zinc-air batteries with superior high power density/energy density and durability is reported for the first time. In micro- and nanoscale, robust 2D architecture together with numerous nanopores inside the nanosheets provides an advantageous micro/nanostructured surface for O2 diffusion and a high electrocatalytic active surface area. In atomic scale, Ni doping significantly enhances the intrinsic oxygen reduction reaction activity per active site. As a result of controlled multiscale structure, the primary zinc-air battery with engineered Ni-doped CoO NSs electrode shows excellent performance with a record-high discharge peak power density of 377 mW cm-2 , and works stable for >400 h at 5 mA cm-2 . Rechargeable zinc-air battery based on Ni-doped CoO NSs affords an unprecedented small charge-discharge voltage of 0.63 V, outperforming state-of-the-art Pt/C catalyst-based device. Moreover, it is shown that Ni-doped CoO NSs assembled into all-solid-state coin cells can power 17 light-emitting diodes and charge an iPhone 7 mobile phone.

Designing Hybrid NiP2/NiO Nanorod Arrays for Efficient Alkaline Hydrogen Evolution.

Transition-metal phosphides (TMPs) have lately drawn intensive attention because of their noble metal-free properties and high catalytic activities for the hydrogen evolution reaction (HER). The current research mainly focuses on the development of TMPs toward the HER in acidic solutions; however, less efforts have been directed to specifically design TMPs for alkaline HER. Here, we design a new bi-functional metal phosphide-oxide catalyst to facilitate the overall multistep HER process in alkaline environments. In this new catalytic system, oxygen-vacancy-rich NiO provides abundant active sites for dissociation of water, and the negatively charged P species in NiP2 facilitate adsorption of hydrogen intermediates. The resulting hybrid NiP2/NiO NRs show excellent alkaline HER catalytic activity and stability. Our work demonstrates that it is highly promising to engineer multiple components in hybrid catalytic systems to enhance the overall reaction kinetics and thus achieve improvements in catalytic performance.