Crystal and Ligand Field Models of Solid Catalysts

Dowden, D. A.

doi:10.1080/01614947208076863

Cited by 51 publications

(20 citation statements)

References 29 publications

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“…Consequently, an M-shaped relationship was obtained, with the maximum performance achieved on La-based perovskite oxide surfaces with d 4 and d 7 configurations (Figure A). This d-electron effect was also observed in gas-phase CO and hydrocarbon oxidation catalysis on perovskite oxides. , To further investigate the d-electron effect, a volcano-shaped behavior plot was attained by correlating the e g electron (σ* orbital occupation) with ORR activity, as shown in Figure B. The e g orbital overlaps strongly with the O-2p σ orbital (Figure C), determining the B–O bond strength during the chemisorption of oxygenated species in ORR.…”

Section: La-based Perovskites As Electrocatalysts For Oxygen Reductio...mentioning

confidence: 64%

Recent Advances of Lanthanum-Based Perovskite Oxides for Catalysis

2015

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There is a need to reduce the use of noble metal elementsespecially in the field of catalysis, where noble metals are ubiquitously applied. To this end, perovskite oxides, an important class of mixed oxide, have been attracting increasing attention for decades as potential replacements. Benefiting from the extraordinary tunability of their compositions and structures, perovskite oxides can be rationally tailored and equipped with targeted physical and chemical propertiesfor example, redox behavior, oxygen mobility, and ionic conductivityfor enhanced catalysis. Recently, the development of highly efficient perovskite oxide catalysts has been extensively studied. This perspective article summarizes the recent development of lanthanum-based perovskite oxides as advanced catalysts for both energy conversion applications and traditional heterogeneous reactions.

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Section: La-based Perovskites As Electrocatalysts For Oxygen Reductio...mentioning

confidence: 64%

Recent Advances of Lanthanum-Based Perovskite Oxides for Catalysis

2015

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“…Hence, based on molecular orbital principles, the number of transition metal d electrons was discussed by Bockris and Otagawa as one of the simplest electronic descriptors [67,68]. Studying a series of AMO 3 (M = Cr, V, Mn, Fe, Co, Ni) perovskite electrocatalysts, the OER overpotential was found to inversely correlate with the enthalpy of hydroxide formation and with the amount of d-electron which is postulated to have a strong influence on the metal-OH* bond strength as well as on the chemisorption of oxygen, as discussed by Dowden et al [69] and recently computed by Calle-Vallejo et al [70]. Furthermore, Dowden also argued that the chemisorption could be affected by the crystal field stabilization energy (CFSE) with different e g occupancy.…”

Section: Low Temperature Oxygen Evolution Reactionmentioning

confidence: 88%

Factors Controlling the Redox Activity of Oxygen in Perovskites: From Theory to Application for Catalytic Reactions

Yang

Grimaud

2017

Catalysts

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Abstract:Triggering the redox reaction of oxygens has become essential for the development of (electro) catalytic properties of transition metal oxides, especially for perovskite materials that have been envisaged for a variety of applications such as the oxygen evolution or reduction reactions (OER and ORR, respectively), CO or hydrocarbons oxidation, NO reduction and others. While the formation of ligand hole for perovskites is well-known for solid state physicists and/or chemists and has been widely studied for the understanding of important electronic properties such as superconductivity, insulator-metal transitions, magnetoresistance, ferroelectrics, redox properties etc., oxygen electrocatalysis in aqueous media at low temperature barely scratches the surface of the concept of oxygen ions oxidation. In this review, we briefly explain the electronic structure of perovskite materials and go through a few important parameters such as the ionization potential, Madelung potential, and charge transfer energy that govern the oxidation of oxygen ions. We then describe the surface reactivity that can be induced by the redox activity of the oxygen network and the formation of highly reactive surface oxygen species before describing their participation in catalytic reactions and providing mechanistic insights and strategies for designing new (electro) catalysts. Finally, we give a brief overview of the different techniques that can be employed to detect the formation of such transient oxygen species.

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“…The ligand field approach to the understanding of the catalytic properties of perovskites has been stressed recently [92]. However, already in 1989, Tejuca et al [95] could summarize several results about the role of the occupancy of the B 3d orbital in the LaBO 3 series, where La is a lanthanide (they recalled an early suggestion by Voorhoven [98], in turn referring to early work by Dowden [99]). It was shown that the CO oxidation activity increased when going (in terms of the occupancy of the 3d level of the B 3+ cation) from vanadates to cobaltites, then decreasing again going from cobaltites to ferrites.…”

Section: Perovskitesmentioning

confidence: 99%

How Chemoresistive Sensors Can Learn from Heterogeneous Catalysis. Hints, Issues, and Perspectives

et al. 2021

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The connection between heterogeneous catalysis and chemoresistive sensors is emerging more and more clearly, as concerns the well-known case of supported noble metals nanoparticles. On the other hand, it appears that a clear connection has not been set up yet for metal oxide catalysts. In particular, the catalytic properties of several different oxides hold the promise for specifically designed gas sensors in terms of selectivity towards given classes of analytes. In this review, several well-known metal oxide catalysts will be considered by first exposing solidly established catalytic properties that emerge from related literature perusal. On this basis, existing gas-sensing applications will be discussed and related, when possible, with the obtained catalysis results. Then, further potential sensing applications will be proposed based on the affinity of the catalytic pathways and possible sensing pathways. It will appear that dialogue with heterogeneous catalysis may help workers in chemoresistive sensors to design new systems and to gain remarkable insight into the existing sensing properties, in particular by applying the approaches and techniques typical of catalysis. However, several divergence points will appear between metal oxide catalysis and gas-sensing. Nevertheless, it will be pointed out how such divergences just push to a closer exchange between the two fields by using the catalysis knowledge as a toolbox for investigating the sensing mechanisms.

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Crystal and Ligand Field Models of Solid Catalysts

Cited by 51 publications

References 29 publications

Recent Advances of Lanthanum-Based Perovskite Oxides for Catalysis

Recent Advances of Lanthanum-Based Perovskite Oxides for Catalysis

Factors Controlling the Redox Activity of Oxygen in Perovskites: From Theory to Application for Catalytic Reactions

How Chemoresistive Sensors Can Learn from Heterogeneous Catalysis. Hints, Issues, and Perspectives

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