Synthetically tuning the surface properties of many oxide catalysts to optimize their catalytic activity has been appreciably challenging given their complex crystal structure.Nickelate oxides (e.g., La2NiO4+δ) are among complex, layered oxides with great potential toward efficiently catalyzing chemical/electrochemical reactions involving oxygen (oxygen reduction, ammonia oxidation). Our theoretical calculations show that the surface structure of La2NiO4+δ plays a critical role in its activity, with (001)-Ni oxide terminated surface being the most active. This is demonstrated through the effect on the energetics associated with surface oxygen exchange -key process in reactions involving oxygen on these oxides. Using a reverse microemulsion method, we have synthesized La2NiO4+δ nanorod-structured catalysts highly populated by (001)-Ni oxide terminated surfaces. We show that these nanostructures exhibit superior catalytic activity toward oxygen exchange/reduction as compared to the traditional catalysts, while maintaining stability under reaction conditions. The findings reported here pave the way for engineering complex metal oxides with optimal activity.

Dwindling fossil fuel resources and substantial release of CO2 from their processing have increased the appeal to use biomass as a sustainable platform for synthesis of chemicals and fuels. Steps toward this will require selective upgrading of biomass to suitable intermediates. Traditionally, biomass upgrading has involved thermochemical processes that require excessive amounts of petrochemical-derived H2 and suffer from poor product selectivity. Electrochemical routes have emerged as promising alternatives because of ( a) the replacement of petrochemical-derived H2 by protons generated in situ, ( b) mild operating temperatures and pressures, and ( c) the use of electrode potential to tune reaction rates and product selectivity. In this review, we highlight the advances in the electrocatalytic hydrogenation and oxidation of biomass-derived platform molecules. The effects of important reaction parameters on electrochemical efficiency and catalytic activity/selectivity are thoroughly discussed. We conclude by summarizing current challenges and discussing future research directions.

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Oxygen electrocatalysis plays a critical role in the efficiency of important energy conversion and storage systems. While many efforts have focused on designing efficient electrocatalysts for these processes, optimal catalysts that are inexpensive, active, selective, and stable are still being searched. Nonstoichiometric, mixed-metal oxides present a promising group of electrocatalysts for these processes due to the versatility of the surface composition and fast oxygen conducting properties. Herein, we demonstrate, using a combination of theoretical and experimental studies, the ability to develop design principles that can be used to engineer oxygen electrocatalysis activity of layered, mixed ionic-electronic conducting Ruddlesden-Popper (R-P) oxides. We show that a density function theory (DFT) derived descriptor, O binding energy on a surface oxygen vacancy, can be effective in identifying efficient R-P oxide structures for oxygen reduction reaction (ORR). Using a controlled synthesis method, well-defined nanostructures of R-P oxides are obtained, which along with thermochemical and electrochemical activity studies are used to validate the design principles. This has led to the identification of a highly active ORR electrocatalyst, nanostructured Co-doped lanthanum nickelate oxide, which when incorporated in solid oxide fuel cell cathodes significantly enhances the performance at intermediate temperatures (∼550 °C), while maintaining long-term stability. The reported findings demonstrate the effectiveness of the developed design principles to engineer mixed ionic-electronic conducting oxides for efficient oxygen electrocatalysis, and the potential of nanostructured Co-doped lanthanum nickelate oxides as promising catalysts for oxygen electrocatalysis.

The oxidative degradation rates of a CO 2 sorbent composed of a mesoporous alumina impregnated with poly-(ethylenimine) (PEI) are measured under systematically varied conditions and a reaction rate law is created. Good agreement is shown between the rate of oxidation obtained via in situ calorimetric heat measurement during oxidative degradation reactions and the loss of CO 2 capture performance presented as amine efficiency (mol CO 2 /mol amine). PEI mass loss and elemental composition are tracked over the course of the reaction and used in conjunction with the oxidation rate measurements to shed insight into the oxidation reaction(s). These data, in combination with measurements of the heat of reaction, suggest a common reaction set across the range of temperatures, oxygen concentrations, and sorbent compositions tested. The data are consistent with the basic autoxidation scheme (BAS), the accepted mechanism of autoxidation of aliphatic polymers. We propose a lumped kinetic model to describe the oxidation reaction set and estimate an activation energy of 105 kJ/mol and an oxygen reaction order of 0.5−0.7 from the data accordingly. These parameters can be incorporated into process cycle models to estimate the material lifetime, a critical uncertainty in the deployment of DAC technologies.