• Energy Research

The selective catalytic oxidation of NH3 (NH3-SCO) to N2 is an important reaction for the treatment of diesel engine exhaust. Co3O4 has the highest activity among non-noble metals but suffers from N2O release. Such N2O emissions have recently been regulated due to having a 300× higher greenhouse gas effect than CO2. Here, we design CuO-supported Co3O4 as a cascade catalyst for the selective oxidation of NH3 to N2. The NH3-SCO reaction on CuO-Co3O4 follows a de-N2O pathway. Co3O4 activates gaseous oxygen to form N2O. The high redox property of the CuO-Co3O4 interface promotes the breaking of the N-O bond in N2O to form N2. The addition of CuO-Co3O4 to the Pt-Al2O3 catalyst reduces the full NH3 conversion temperature by 50 K and improves the N2 selectivity by 20%. These findings provide a promising strategy for reducing N2O emissions and will contribute to the rational design and development of non-noble metal catalysts.

AbstractWith the ongoing developments in biomass conversion, the oxidation of bioethanol to acetaldehyde may become a favorable and green alternative to the preparation from ethylene. Here, a simple and effective method to encapsulate gold nanoparticles in zeolite silicalite‐1 is reported and their high activity and selectivity for the catalytic gas‐phase oxidation of ethanol are demonstrated. The zeolites are modified by a recrystallization process, which creates intraparticle voids and mesopores that facilitate the formation of small and disperse nanoparticles upon simple impregnation. The individual zeolite crystals comprise a broad range of mesopores and contain up to several hundred gold nanoparticles with a diameter of 2–3 nm that are distributed inside the zeolites rather than on the outer surface. The encapsulated nanoparticles have good stability and result in 50 % conversion of ethanol with 98 % selectivity toward acetaldehyde at 200 °C, which (under the given reaction conditions) corresponds to 606 mol acetaldehyde/mol Au hour−1.

Abstract Metal foam flow-fields have shown great potential in improving the uniformity of reactant distribution in polymer electrolyte fuel cells (PEFCs) by eliminating the ‘land/channel’ geometry of conventional designs. However, a detailed understanding of the water management in operational metal foam flow-field based PEFCs is limited. This study aims to provide the first clear evidence of how and where water is generated, accumulated and removed in the metal foam flow-field based PEFCs using in-operando neutron radiography, and correlate the water ‘maps’ with electrochemical performance and durability. Results show that the metal foam flow-field based PEFC has greater tolerance to dehydration at 1000 mA cm−2, exhibiting a ~50% increase in voltage, ~127% increase in total water mass and ~38% decrease in high frequency resistance (HFR) than serpentine flow-field design. Additionally, the metal foam flow-field promotes more uniform water distribution where the standard deviation of the liquid water thickness distribution across the entire cell active area is almost half that of the serpentine. These superior characteristics of metal foam flow-field result in greater than twice the maximum power density over serpentine flow-field. Results suggest that optimizing fuel cell operating condition and foam microstructure would partly mitigate flooding in the metal foam flow-field based PEFC.

AbstractInorganic solid‐state electrolytes (SSEs) are nonflammable alternatives to the commercial liquid‐phase electrolytes. This enables the use of lithium (Li) metal as an anode, providing high‐energy density and improved stability by avoiding unwanted liquid‐phase chemical reactions. Among the different types of SSEs, the garnet‐type electrolytes witness a rapid development and are considered as one of the top candidates to pair with Li metal due to their high ionic conductivity, thermal, and electrochemical stability. However, the large resistances at the interface between garnet‐type electrolytes and cathode/anode are the major bottlenecks for delivering desirable electrochemical performances of all‐solid‐state batteries (SSBs). The electrolyte/anode interface also suffers from metallic dendrite formation, leading to rapid performance degradation. This is a fundamental material challenge due to the poor contact and wettability between garnet‐type electrolytes with electrode materials. Here, we summarize and analyze the recent contributions in mitigating such materials challenges at the interface. Strategies used to address these challenges are divided into different categories with regard to their working principles. On one hand, progress has been made in the anode/garnet interface, such as the successful application of Li‐alloy anode and different artificial interlayers, significantly improving interfacial performance. On the other hand, the desired cathode/garnet interface is still hard to reach due to the complex chemical and physical structure at the cathode. The common methods used are nanostructured cathode host and sintering additives for increasing the contact area. On the basis of this information, we present our views on the remaining challenges and future research of electrode/garnet interface. This review not only motivates the need for further understanding of the fundamentals, stability, and modifications of the garnet/electrode interfaces but also provides guidelines for the future design of the interface for SSB.

Surface oxidation chemistry involves the formation and breaking of metal-oxygen (M-O) bonds. Ideally, the M-O bonding strength determines the rate of oxygen absorption and dissociation. Here, we design reactive bridging O2- species within the atomic Cu-O-Fe site to accelerate such oxidation chemistry. Using in situ X-ray absorption spectroscopy at the O K-edge and density functional theory calculations, it is found that such bridging O2- has a lower antibonding orbital energy and thus weaker Cu-O/Fe-O strength. In selective NH3 oxidation, the weak Cu-O/Fe-O bond enables fast Cu redox for NH3 conversion and direct NO adsorption via Cu-O-NO to promote N-N coupling toward N2. As a result, 99% N2 selectivity at 100% conversion is achieved at 573 K, exceeding most of the reported results. This result suggests the importance to design, determine, and utilize the unique features of bridging O2- in catalysis.

AbstractThe key to develop earth‐abundant energy storage technologies sodium‐ and potassium‐ion batteries (SIBs and PIBs) is to identify low‐cost electrode materials that allow fast and reversible Na+/K+ intercalation. Here, we report an intercalation‐type material TiNb24O62 as a versatile anode for SIBs and PIBs, via a synergistic strategy of oxygen vacancy and carbon incorporation to enhance ion and electron diffusion. The TiNb24O62−x/reduced graphene oxide (rGO) composite anode delivers high reversible capacities (130 mA h g−1 for SIBs and 178 mA h g−1 for PIBs), great rate performance (54 mA h g−1 for SIBs and 37 mA h g−1 for PIBs at 1 A g−1), and superior cycle stability (73.7% after 500 cycles for SIBs and 84% after 300 cycles for PIBs). The performance is among the best results of intercalation‐type metal oxide anodes for SIBs and PIBs. The better performance of TiNb24O62−x/rGO in SIBs than PIBs is due to the better reaction kinetics of the former. Moreover, mechanistic study confirms that the redox activity of Nb4+/5+ is responsible for the reversible intercalation of Na+/K+. Our results suggest that TiNb24O62−x/rGO is a promising anode for SIBs and PIBs and may stimulate further research on intercalation‐type compounds as candidate anodes for large ion batteries.

The wide-scale expansion of renewable energy sources has triggered the demand for advanced energy storage technologies. Aqueous zinc ion batteries (AZIBs) have been widely noticed in recent years because of their intrinsic safety, abundant raw materials, and environmental friendliness. Among the reported cathode materials for ZIBs, Mn-oxide materials stand out as one of the most promising candidates with their diverse structures, high capacity, and cost-effectiveness. However, the complex energy storage mechanism and unstable electrochemical properties persistently obstruct the practical application of this technology. It has been realized that these disturbances are related to the structural evolution of Mn-oxide materials during the charge/discharge process, and considerable relevant research was carried out. In this review, we present an up-to-date review of the most recent advancements and challenges concerning Mn-oxide cathode materials for aqueous zinc ion batteries. Firstly, we offer a concise summary and categorization of several widely recognized energy storage mechanisms and crystal structures. Then, we focused on sorting out the structural evolution path of Mn-oxide materials, and explored the relevant influencing factors and the relationship between phase evolution and property fluctuations. Finally, we distill key optimization strategies and provide a forward-looking perspective on future research.