Complexity in strongly correlated oxides such as perovskite strictly dominates their performance for oxygen reduction reaction (ORR). Precise control of the physical correlations among spin, charge, orbital, and lattice degrees of freedom in these oxides can exercise considerable enhancement of ORR activity, but has until now remained elusive. Here, we show that nonmagnetic hexavalent molybdenum (Mo⁶⁺) atomically dispersed within oxide lattice steers the intrinsic activity of catalytically active sites by entrapping extrinsic electrons at their 3d orbitals, without the occurrence of lattice symmetry breaking and magnetic perturbation. With double perovskite La₂Co²⁺Mn⁴⁺O₆ as a model catalyst, the atomic-scale electron trap generates additional high-spin, catalytically active Mn³⁺(t³ _2ge¹ _g) sites and highly conductive Co²⁺(e² _g)–O–Mn³⁺(e¹ _g) double exchange channels, leading to five-fold improvement in ORR activity. First-principles calculations reveal a substantial increase of the spin density on Mn sites caused by electron trapping, and unambiguously confirm a more exothermic reaction pathway as well as a lower barrier of the rate-limiting surface hydroxide regeneration on Mo₁/La₂CoMnO₆. We can also extend this strategy with atomic precision easily to other four oxide catalysts and achieve large enhancement in their ORR activities as anticipated, indicating its broad utility. This work embodies the theories of condensed matter physics in rational design of ORR catalysts, and may inspire further development of the control of electron correlation in strongly correlated electron systems.

Nanoporous gold (NPG) is characterized by a bicontinuous network of nanometer-sized metallic struts and interconnected pores formed spontaneously by oxidative dissolution of the less noble element from gold alloys. The resulting material exhibits decent catalytic activity for low-temperature, aerobic total as well as partial oxidation reactions, the oxidative coupling of methanol to methyl formate being the prototypical example. This review not only provides a critical discussion of ways to tune the morphology and composition of this material and its implication for catalysis and electrocatalysis, but will also exemplarily review the current mechanistic understanding of the partial oxidation of methanol using information from quantum chemical studies, model studies on single-crystal surfaces, gas phase catalysis, aerobic liquid phase oxidation, and electrocatalysis. In this respect, a particular focus will be on mechanistic aspects not well understood, yet. Apart from the mechanistic aspects of catalysis, best practice examples with respect to material preparation and characterization will be discussed. These can improve the reproducibility of the materials property such as the catalytic activity and selectivity as well as the scope of reactions being identified as the main challenges for a broader application of NPG in target-oriented organic synthesis.

Recently, several forms of unsupportedgold were shown to display a remarkable activity to catalyze oxidation reactions. Experimental evidence points to the crucial role of residual silver present in very small concentrations in these novel catalysts. We focus on the catalytic properties of nanoporous gold (np-Au) foams probed viaCO and oxygen adsorption/co-adsorption. Experimental results are analyzed using theoretical models represented by the flat Au(111) and the kinked Au(321) slabs with Ag impurities. We show that Ag atoms incorporated into gold surfaces can facilitate the adsorption and dissociation of molecular oxygen on them. CO adsorbed on top of 6-fold coordinated Au atoms can in turn be stabilized by co-adsorbed atomic oxygen by up to 0.2 eV with respect to the clean unsubstituted gold surface. Our experiments suggest a linking of that most strongly bound CO adsorption state to the catalytic activity of np-Au. Thus, our results shed light on the role of silver admixtures in the striking catalytic activity of unsupported gold nanostructures.

We review systematic experimental and theoretical efforts that explored formation, structure and reactivity of PdZn catalysts for methanol steam reforming, a material recently proposed to be superior to the industrially used Cu based catalysts. Experimentally, ordered surface alloys with a Pd : Zn ratio of ∼1 : 1 were prepared by deposition of thin Zn layers on a Pd(111) surface and characterized by photoelectron spectroscopy and low-energy electron diffraction. The valence band spectrum of the PdZn alloy resembles closely the spectrum of Cu(111), in good agreement with the calculated density of states for a PdZn alloy of 1 : 1 stoichiometry. Among the issues studied with the help of density functional calculations are surface structure and stability of PdZn alloys and effects of Zn segregation in them, and the nature of the most likely water-related surface species present under the conditions of methanol steam reforming. Furthermore, a series of elementary reactions starting with the decomposition of methoxide, CH₃O, along both C–H and C–O bond scission channels, on various surfaces of the 1 : 1 PdZn alloy [planar (111), (100) and stepped (221)] were quantified in detail thermodynamically and kinetically in comparison with the corresponding reactions on the surfaces Pd(111) and Cu(111). The overall surface reactivity of PdZn alloy was found to be similar to that of metallic Cu. Reactive methanol adsorption was also investigated by in situ X-ray photoelectron spectroscopy for pressures between 3 × 10⁻⁸ and 0.3 mbar.