Ongoing research to develop advanced electrocatalysts for the oxygen evolution reaction (OER) is needed to address demand for efficient energy conversion and carbon-free energy sources. In the OER process, acidic electrolytes have higher proton concentration and faster response than alkaline ones, but their harsh strongly acidic environment requires catalysts with greater corrosion and oxidation resistance. At present, iridium oxide (IrO2) with its strong stability and excellent catalytic performance is the catalyst of choice for the anode side of commercial PEM electrolysis cells. However, the scarcity and high cost of iridium (Ir) and the unsatisfactory activity of IrO2 hinder industrial scale application and the sustainable development of acidic OER catalytic technology. This highlights the importance of further research on acidic Ir-based OER catalysts. In this review, recent advances in Ir-based acidic OER electrocatalysts are summarized, including fundamental understanding of the acidic OER mechanism, recent insights into the stability of acidic OER catalysts, highly efficient Ir-based electrocatalysts, and common strategies for optimizing Ir-based catalysts. The future challenges and prospects of developing highly effective Ir-based catalysts are also discussed.

The interactions between the catalyst and support are widely used in many important catalytic reactions but the construction of strong interaction with definite microenvironments to understand the structure-activity relationship is still challenging. Here, strongly-interacted composites are prepared via selective exsolution of active NiSe2 from the host matrix of NiFe2O4 (S-NiSe2/NiFe2O4) taking advantage of the differences of migration energy, in which the NiSe2 possessed both high dispersion and small size. The characteristics of spatially resolved scanning transmission X-ray microscopy (STXM) coupled with analytical Mössbauer spectra for the surface and bulk electronic structures unveiled that this strongly interacted composite triggered more charge transfers from the NiSe2 to the host of NiFe2O4 while stabilizing the inherent atomic coordination of NiFe2O4. The obtained S-NiSe2/NiFe2O4 exhibits overpotentials of 290 mV at 10 mA cm-2 for oxygen evolution reaction (OER). This strategy is general and can be extended to other supported catalysts, providing a powerful tool for modulating the catalytic performance of strongly-interacted composites.

Metal-semiconductor heterostructured catalysts have attracted great attention because of their unique interfacial characteristics and superior catalytic performance. Exsolution of nanoparticles is one of the effective and simple ways for in-situ growth of metal nanoparticles embedded in oxide surfaces and their favorable dispersion and stability. However, both high-temperature and a reducing atmosphere are required simultaneously in conventional exsolution, which is time-consuming and costly, and particles often agglomerate during the process. In this work, Ca0.9Ti0.8Ni0.1Fe0.1O3-δ (CTNF) is exposed to dielectric blocking discharge (DBD) plasma at room temperature to fabricate alloying FeNi3 nanoparticles from CTNF perovskite. FeNi3-CTNF has outstanding catalytic activity for photothermal reverse water gas shift reaction (RWGS). At 350 °C under full-spectrum irradiation, the carbon monoxide (CO) yield of FeNi3-CTNF (10.78 mmol g-1 h-1) is 11 times that of pure CaTiO3(CTO), and the CO selectivity is 98.9%. This superior catalytic activity is attributed to the narrow band gap, photogenerated electron migration to alloy particles, and abundant surface oxygen vacancies. The carbene pathway reaction is also investigated through in-situ Raman spectroscopy. The present work presents a straightforward method for the exsolution of nanoalloys in metal-semiconductor heterostructures for photothermal CO2 reduction.

Nanoparticle (NP) exsolution from perovskite-based oxides matrix upon reduction has emerged as an ideal platform for designing highly active catalysts for energy and environmental applications. However, the mechanism of how the material characteristics impacts the activity is still ambiguous. In this work, taking Pr0.4Sr0.6Co0.2Fe0.7Nb0.1O3 thin film as the model system, we demonstrate the critical impact of the exsolution process on the local surface electronic structure. Combining advanced microscopic and spectroscopic techniques, particularly scanning tunneling microscopy/spectroscopy and synchrotron-based near ambient X-ray photoelectron spectroscopy, we find that the band gaps of both the oxide matrix and exsolved NP decrease during exsolution. Such changes are attributed to the defect state within the forbidden band introduced by oxygen vacancies and the charge transfer across the NP/matrix interface. Both the electronic activations of oxide matrix and the exsolved NP phase lead to good electrocatalytic activity toward the fuel oxidation reaction at elevated temperature.

The in situ exsolution technique of nanoparticles has brought new opportunities for the utilization of perovskite-based catalysts in solid oxide cells. However, the lack of control over the structural evolution of host perovskites during the promotion of exsolution has restricted the architectural exploitation of exsolution-facilitated perovskites. In this study, we strategically broke the long-standing trade-off phenomenon between promoted exsolution and suppressed phase transition via B-site supplement, thus broadening the scope of exsolution-facilitated perovskite materials. Using carbon dioxide electrolysis as an illustrative case study, we demonstrate that the catalytic activity and stability of perovskites with exsolved nanoparticles (P-eNs) can be selectively enhanced by regulating the explicit phase of host perovskites, accentuating the critical role of the architectures of perovskite scaffold in catalytic reactions occurring on P-eNs. The concept demonstrated could potentially pave the way for designing the advanced exsolution-facilitated P-eNs materials and unveiling a wide range of catalytic chemistry taking place on P-eNs.

The exsolution of nanoparticles (NPs) on material surfaces exhibits good performance with great potential in the field of catalysis. In this study, a method with twice lasers treatment (TLT) is proposed for the first time to rapidly promote the exsolution of Co NPs to the surface of (La0.7Sr0.3)0.93Ti0.93Co0.07O3(LSTC) by laser rapid heating to enhance the electrochemical performance of the LSTC. The entire process from precursor powder-stable perovskite crystal structure-Co NPs exsolution on the LSTC surface takes only ≈36 s by TLT. The Co NPs exsolution was confirmed by x-ray diffractometer, scanning electron microscopy and high-resolution transmission electron microscopy. After TLT, a large number of Co NPs reached 75 particlesμm-2appeared on the surface of LSTC with the onset potential of 1.38 V, the overpotential of 214 mV, and the Tafel slope of 81.14 mV dec-1, showing good catalytic activity and long-term stability. The novel process of using TLT to rapidly induce exsolution of NPs enables the rapid preparation of nanoparticle-decorated perovskite materials with better electrochemical properties, thus enriching exsolution technology and opening a new avenue for surface science research.

In order to clarify the role of R2O3 in the metal-oxide catalysts derived from complex oxide precursors, a series of R1.5Ca0.5NiO4 (R = Nd, Sm, Eu) complex oxides was obtained. A significant systematic increase in the orthorhombic distortion of the R1.5Ca0.5NiO4 structure (K2NiF4 type, Cmce) from Nd to Eu correlates with a corresponding decrease in their ionic radii. A reduction of R1.5Ca0.5NiO4 in the Ar/H2 gas mixture at 800 °C causes a formation of dense agglomerates of CaO and R2O3 coated with spherical 25-30 nm particles of Ni metal. The size of metal particles and oxide agglomerates is similar in all Ni/(R2O3,CaO) composites in the study. Their morphology is rather similar to the products of redox exsolution obtained by the partial reduction of complex oxides. All obtained composites demonstrated a significant catalytic activity in the dry reforming (DRM) and partial oxidation (POM) of methane at 700-800 °C. A systematic decrease in the DRM catalytic activity of composites from Nd to Eu could be attributed to the basicity reduction of R2O3 components of the composite catalysts. The maximum CH4 conversion in POM reaction was observed for Ni/(Sm2O3,CaO), while the maximum selectivity was demonstrated by Nd2O3-based composite. The possible reasons for the observed difference are discussed.

Dry reforming of methane (DRM) has been emerging as a viable solution to achieving carbon neutrality enhanced by the Paris Agreement as it converts the greenhouse gases of CO2 and CH4 into industrially useful syngas. However, there have been limited studies on the DRM catalyst under mild operating conditions with a high dilution gas ratio due to their deactivation from carbon coking and metal sintering. Herein, we apply the triple-phase boundary (TPB) concept to DRM catalyst via exsolution phenomenon that can secure elongated TPB by controlling the Fe-doping ratio in perovskite oxide. Remarkably, the exsolved catalyst with prolongated TPB shows exceptional CO2 and CH4 conversion rates of 95.9 % and 91.6 %, respectively, stable for 1000 hours under a dilution-free system. DFT calculations confirm that the Lewis acid of support and Lewis base of metal at the TPB promote the adsorption of reactants, resulting in lowering the overall CO2 dissociation and CH4 dehydrogenation energy.

Perovskite materials with exsolved nanoparticles have a wide range of applications in energy conversion systems owing to their unique basal plane active sites and excellent catalytic properties. The introduction of A-site deficiency can help the formation of highly mobile oxygen vacancies and remarkably enhance the reducibility of Ni nanoparticles, thus significantly increasing electronic conductivity and catalytic activity simultaneously. Herein, we adopt pulsed electric current (PEC) treatment, a novel approach instead of the long-time high-temperature reduction technique, and for the first time review that the exsolution of minuscule Ni nanoparticles (8-20 nm) could be facilitated on Ni-doped La0.52Sr0.28Ti0.94Ni0.06O3(LSTN) anodes with A-site deficiency. Encouragingly, finding that low PEC can successfully lead to nanoparticle exsolution and show a significantly improved oxygen evolution reaction performance of LSTN-PEC (LSTN after PEC treatment) possessing A-site deficiency, the onset potential of LSTN-PEC (500 V) (LSTN after PEC treatment with 500 V-4 Hz-90 s) was advanced by 0.173 V, theRctvalue was reduced by 82.38 Ω·cm2, and the overpotential was also reduced by 73 mV.

Anode-supported protonic ceramic fuel cells (PCFCs) are highly promising and efficient energy conversion systems. However, several challenges need to be overcome before these systems are used more widely, including the poor sintering of recently developed proton-conducting oxides and the decreased proton conductivity due to detrimental reactions between the nickel from anode and the electrolyte occurring during high-temperature co-sintering. Herein, a Ni doping strategy to increase the electrolyte sintering, suppress the detrimental phase reactions, and generate stable Ni nanoparticles for enhanced performance is proposed. A nickel-doped perovskite oxide is developed with the nominal composition of Ba(Zr0.1 Ce0.7 Y0.1 Yb0.1 )0.95 Ni0.05 O3- δ . Acting as a sintering aid, such a small amount of nickel effectively improves the sintering of the electrolyte. Concomitantly, reactions between nickel and the Ni-doped ceramic phase are suppressed, turning detrimental phase reactions into benefits. The nickel doping further promotes the formation of Ni nanoparticles, which enhance the electrocatalytic activity of the anode toward the hydrogen oxidation reaction and improve the charge transfer across the anode-electrolyte interface. As a result, highly efficient PCFCs are developed. The innovative anode developed in this work also shows favorable activity toward ammonia decomposition, making it highly promising for use in direct ammonia fuel cells.