Mathematical Model-Assisted Ultrasonic Spray Coating for Scalable Production of Large-Sized Solid Oxide Electrochemical Cells.

Thin solid oxide films are crucial for developing high-performance solid oxide-based electrochemical devices aimed at decarbonizing the global energy system. Among various methods, ultrasonic spray coating (USC) can provide the throughput, scalability, quality consistency, roll-to-roll compatibility, and low material waste necessary for scalable production of large-sized solid oxide electrochemical cells. However, due to the large number of USC parameters, systematic parameter optimization is required to ensure optimal settings. However, the optimizations in previous literature are either not discussed or not systematic, facile, and practical for scalable production of thin oxide films. In this regard, we propose an USC optimization process assisted with mathematical models. Using this method, we obtained optimal settings for producing high-quality, uniform 4 × 4 cm2 oxygen electrode films with a consistent thickness of ∼27 µm in 1 min in a facile and systematic way. The quality of the films is evaluated at both micrometer and centimeter scales and meets desirable thickness and uniformity criteria. To validate the performance of USC-fabricated electrolytes and oxygen electrodes, we employ protonic ceramic electrochemical cells, which achieve a peak power density of 0.88 W cm-2 in the fuel cell mode and a current density of 1.36 A cm-2 at 1.3 V in the electrolysis mode, with minimal degradation over a period of 200 h. These results demonstrate the potential of USC as a promising technology for scalable production of large-sized solid oxide electrochemical cells.

Inducing Covalent Atomic Interaction in Intermetallic Pt Alloy Nanocatalysts for High-Performance Fuel Cells.

The harsh working environments of proton exchange membrane fuel cells (PEMFCs) pose huge challenges to the stability of Pt-based alloy catalysts. The widespread presence of metallic bonds with significantly delocalized electron distribution often lead to component segregation and rapid performance decay. Here we report L10 -Pt2 CuGa intermetallic nanoparticles with a unique covalent atomic interaction between Pt-Ga as high-performance PEMFC cathode catalysts. The L10 -Pt2 CuGa/C catalyst shows superb oxygen reduction reaction (ORR) activity and stability in fuel cell cathode (mass activity=0.57 A mgPt -1 at 0.9 V, peak power density=2.60/1.24 W cm-2 in H2 -O2 /air, 28 mV voltage loss at 0.8 A cm-2 after 30 000 cycles). Theoretical calculations reveal the optimized adsorption of oxygen intermediates via the formed biaxial strain on L10 -Pt2 CuGa surface, and the durability enhancement stems from the stronger Pt-M bonds than those in L11 -PtCu resulted from Pt-Ga covalent interactions.

Effective Approaches for Designing Stable M-Nx /C Oxygen-Reduction Catalysts for Proton-Exchange-Membrane Fuel Cells.

The large-scale commercialization of proton-exchange-membrane fuel cells (PEMFCs) is extremely limited by their costly platinum-group metals (PGMs) catalysts, which are used for catalyzing the sluggish oxygen reduction reaction (ORR) kinetics at the cathode. Among the reported PGM-free catalysts so far, metal-nitrogen-carbon (M-Nx /C) catalysts hold a great potential to replace PGMs catalysts for the ORR due to their excellent initial activity and low cost. However, despite tremendous progress in this field in the past decade, their further applications are restricted by fast degradation under practical conditions. Herein, the theoretical fundamentals of the stability of the M-Nx /C catalysts are first introduced in terms of thermodynamics and kinetics. The primary degradation mechanisms of M-Nx /C catalysts and the corresponding mitigating strategies are discussed in detail. Finally, the current challenges and the prospects for designing highly stable M-Nx /C catalysts are outlined.

Engineering the atomic arrangement of bimetallic catalysts for electrochemical CO2 reduction.

The electrochemical CO2 reduction reaction (CO2RR) to form highly valued chemicals is a sustainable solution to address the environmental issues caused by excessive CO2 emissions. Generally, it is challenging to achieve high efficiency and selectivity simultaneously in the CO2RR due to multi-proton/electron transfer processes and complex reaction intermediates. Among the studied formulations, bimetallic catalysts have attracted significant attention with promising activity, selectivity, and stability. Engineering the atomic arrangement of bimetallic nanocatalysts is a promising strategy for the rational design of structures (intermetallic, core/shell, and phase-separated structures) to improve catalytic performance. This review summarizes the recent advances, challenges, and opportunities in developing bimetallic catalysts for the CO2RR. In particular, we firstly introduce the possible reaction pathways on bimetallic catalysts concerning the geometric and electronic properties of intermetallic, core/shell, and phase-separated structures at the atomic level. Then, we critically examine recent advances in crystalline structure engineering for bimetallic catalysts, aiming to establish the correlations between structures and catalytic properties. Finally, we provide a perspective on future research directions, emphasizing current challenges and opportunities.

Carbon-Supported Single Metal Site Catalysts for Electrochemical CO2 Reduction to CO and Beyond.

The electrochemical CO2 reduction reaction (CO2 RR) is a promising strategy to achieve electrical-to-chemical energy storage while closing the global carbon cycle. The carbon-supported single-atom catalysts (SACs) have great potential for electrochemical CO2 RR due to their high efficiency and low cost. The metal centers' performance is related to the local coordination environment and the long-range electronic intercalation from the carbon substrates. This review summarizes the recent progress on the synthesis of carbon-supported SACs and their application toward electrocatalytic CO2 reduction to CO and other C1 and C2 products. Several SACs are involved, including MNx catalysts, heterogeneous molecular catalysts, and the covalent organic framework (COF) based SACs. The controllable synthesis methods for anchoring single-atom sites on different carbon supports are introduced, focusing on the influence that precursors and synthetic conditions have on the final structure of SACs. For the CO2 RR performance, the intrinsic activity difference of various metal centers and the corresponding activity enhancement strategies via the modulation of the metal centers' electronic structure are systematically summarized, which may help promote the rational design of active and selective SACs for CO2 reduction to CO and beyond.

Advanced Electrocatalysis for Energy and Environmental Sustainability via Water and Nitrogen Reactions.

Clean and efficient energy storage and conversion via sustainable water and nitrogen reactions have attracted substantial attention to address the energy and environmental issues due to the overwhelming use of fossil fuels. These electrochemical reactions are crucial for desirable clean energy technologies, including advanced water electrolyzers, hydrogen fuel cells, and ammonia electrosynthesis and utilization. Their sluggish reaction kinetics lead to inefficient energy conversion. Innovative electrocatalysis, i.e., catalysis at the interface between the electrode and electrolyte to facilitate charge transfer and mass transport, plays a vital role in boosting energy conversion efficiency and providing sufficient performance and durability for these energy technologies. Herein, a comprehensive review on recent progress, achievements, and remaining challenges for these electrocatalysis processes related to water (i.e., oxygen evolution reaction, OER, and oxygen reduction reaction, ORR) and nitrogen (i.e., nitrogen reduction reaction, NRR, for ammonia synthesis and ammonia oxidation reaction, AOR, for energy utilization) is provided. Catalysts, electrolytes, and interfaces between the two within electrodes for these electrocatalysis processes are discussed. The primary emphasis is device performance of OER-related proton exchange membrane (PEM) electrolyzers, ORR-related PEM fuel cells, NRR-driven ammonia electrosynthesis from water and nitrogen, and AOR-related direct ammonia fuel cells.

Conductive Porous Laminated Vanadium Nitride as Carbon-Free Hosts for High-Loading Sulfur Cathodes in Lithium-Sulfur Batteries.

Improving the sulfur loading in cathodes is a significant challenge for practical lithium-sulfur batteries. Although carbonaceous sulfur hosts can achieve higher sulfur content and loading, the low tap densities of carbonaceous materials lead to low volumetric energy densities, restricting practical application. Here, conductive porous laminated vanadium nitride (VN) as a carbon-free sulfur host has been successfully developed to construct high tap density, high sulfur loading, and high energy density sulfur electrodes. The laminated stacking multiscale VN featuring interconnected holes possesses high storage space for sulfur loading, achieving high sulfur loading and utilization. VN@S materials' sulfur content and tap density can achieve 80 wt % and 1.17 g cm-3, respectively. At the sulfur loading of 1.0 mg cm-2, the VN@S cathode reaches the reversible capacity of 790 mAh g-1 at 1 C after 200 cycles and 145.2 mAh g-1 at 15 C after 500 cycles. Precisely, at a high sulfur loading of 12.6 mg cm-2, the VN@S cathode delivers a reversible capacity of 518.8 mAh g-1 (485.6 mAh cm-3) at 0.1 C after 100 cycles.

Defect-Rich Copper-doped Ruthenium Hollow Nanoparticles for Efficient Hydrogen Evolution Electrocatalysis in Alkaline Electrolyte.

It is of great importance to develop highly efficient and stable Pt-free catalysts for electrochemical hydrogen generation from water electrolysis. Here, monodisperse 7.5 nm copper-doped ruthenium hollow nanoparticles (NPs) with abundant defects and amorphous/crystalline hetero-phases were prepared and employed as efficient hydrogen evolution electrocatalysts in alkaline electrolyte. Specifically, these NPs only require a low overpotential of 25 mV to achieve a current density of 10 mA cm-2 in 1.0 M KOH and show acceptable stability after 2000 potential cycles, which represents one of the best Ru-based electrocatalysts for hydrogen evolution. Mechanism analysis indicates that Cu incorporation can modify the electronic structure of Ru shell, thereby optimizing the energy barrier for water adsorption and dissociation processes or H adsorption/desorption. Cu doping paired with the defect-rich and highly open hollow structure of the NPs greatly enhances hydrogen evolution activity.

Atomically dispersed metal-nitrogen-carbon catalysts for fuel cells: advances in catalyst design, electrode performance, and durability improvement.

The urgent need to address the high-cost issue of proton-exchange membrane fuel cell (PEMFC) technologies, particularly for transportation applications, drives the development of simultaneously highly active and durable platinum group metal-free (PGM-free) catalysts and electrodes. The past decade has witnessed remarkable progress in exploring PGM-free cathode catalysts for the oxygen reduction reaction (ORR) to overcome sluggish kinetics and catalyst instability in acids. Among others, scientists have identified the newly emerging atomically dispersed transition metal (M: Fe, Co, or/and Mn) and nitrogen co-doped carbon (M-N-C) catalysts as the most promising alternative to PGM catalysts. Here, we provide a comprehensive review of significant breakthroughs, remaining challenges, and perspectives regarding the M-N-C catalysts in terms of catalyst activity, stability, and membrane electrode assembly (MEA) performance. A variety of novel synthetic strategies demonstrated effectiveness in improving intrinsic activity, increasing active site density, and attaining optimal porous structures of catalysts. Rationally designing and engineering the coordination environment of single metal MNx sites and their local structures are crucial for enhancing intrinsic activity. Increasing the site density relies on the innovative strategies of restricting the migration and agglomeration of single metal sites into metallic clusters. Relevant understandings provide the correlations among the nature of active sites, nanostructures, and catalytic activity of M-N-C catalysts at the atomic scale through a combination of experimentation and theory. Current knowledge of the transferring catalytic properties of M-N-C catalysts to MEA performance is limited. Rationally designing morphologic features of M-N-C catalysts play a vital role in boosting electrode performance through exposing more accessible active sites, realizing uniform ionomer distribution, and facilitating mass/proton transports. We outline future research directions concerning the comprehensive evaluation of M-N-C catalysts in MEAs. The most considerable challenge of current M-N-C catalysts is the unsatisfied stability and rapid performance degradation in MEAs. Therefore, we further discuss practical methods and strategies to mitigate catalyst and electrode degradation, which is fundamentally essential to make M-N-C catalysts viable in PEMFC technologies.