CO 2 electroreduction facilitates the sustainable synthesis of fuels and chemicals 1 . Although Cu enables CO 2 -to-multicarbon product (C 2+ ) conversion, the nature of the active sites under operating conditions remains elusive 2 . Importantly, identifying active sites of high-performance Cu nanocatalysts necessitates nanoscale, time-resolved operando techniques [3][4][5] . Here, we present a comprehensive investigation of the structural dynamics during the life cycle of Cu nanocatalysts. A 7 nm Cu nanoparticle ensemble evolves into metallic Cu nanograins during electrolysis, before completely oxidizing to single-crystal Cu 2 O nanocubes upon post-electrolysis air exposure. Operando analytical and four-dimensional (4D) electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) reveals the presence of metallic Cu nanograins under CO 2 reduction conditions. Correlated high-energy-resolution time-resolved Xray spectroscopy suggests that metallic Cu, rich in nanograin boundaries, supports undercoordinated active sites for C-C coupling. The quantitative structure-activity correlation shows a higher fraction of metallic Cu nanograins leads to higher C 2+ selectivity. A 7 nm Cu nanoparticle ensemble, with a unity fraction of active Cu nanograins, exhibits 6 times higher C 2+ selectivity than the 18 nm counterpart with one-third of active Cu nanograins. The correlation of multi-modal operando techniques serves as a powerful platform to advance our fundamental understanding of the complex structural evolution of nanocatalysts under electrochemical conditions.Editor's one-sentence summary: By investigation of structural dynamics during the lifecycle of Cu nanocatalysts, correlation of multimodal operando techniques was found to serve as a powerful platform to advance understanding of their complex structural evolution. Main text:1 Copper remains the only heterogeneous electrocatalyst to selectively catalyze CO 2 reduction reaction (CO 2 RR) to multicarbon (C 2+ ) products, including ethylene, ethanol, and propanol at appreciable rates 1,2 . Recent developments in operando/in situ methods, including advanced electron microscopy and synchrotron-based X-ray methods, provide powerful non-destructive tools to probe active sites and structural changes of electrocatalysts under reaction conditions 3-5 . However, there remains a lingering debate over the active state of Cu catalysts, regarding valence state or coordination environments under CO 2 RR. For instance, some reports have proposed Cu + species and subsurface oxide as possible active sites of oxide-derived Cu electrocatalysts [6][7][8][9] , while others suggested the active state of bulk Cu catalysts is metallic [10][11][12] as subsurface oxides are not stable under negative potentials [13][14][15] . Another possible structural descriptor of locally enhanced CO 2 RR activity has been reported to be micrometer-sized grain boundaries (GBs) on bulk metal electrodes [13][14][15][16][17][18] . Those studies probed the local activity at GBs with a µm-leve...
Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecularlevel thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst−support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free highperformance and durable alkaline fuel cells and related technologies.
Identifying the catalytically active site(s) in the oxygen reduction reaction (ORR), under real-time electrochemical conditions, is critical to the development of fuel cells and other technologies. We have employed in situ synchrotron-based X-ray absorption spectroscopy (XAS) to investigate the synergistic interaction of a Co–Mn oxide catalyst which exhibits impressive ORR activity in alkaline fuel cells. X-ray absorption near edge structure (XANES) was used to track the dynamic structural changes of Co and Mn under both steady state (constant applied potential) and nonsteady state (potentiodynamic cyclic voltammetry, CV). Under steady state conditions, both Mn and Co valences decreased at lower potentials, indicating the conversion from Mn(III,IV) and Co(III) to Mn(II,III) and Co(II), respectively. Rapid X-ray data acquisition, combined with a slow sweep rate in CV, enabled a 3 mV resolution in the applied potential, approaching a nonsteady (potentiodynamic) state. Changes in the Co and Mn valence states were simultaneous and exhibited periodic patterns that tracked the cyclic potential sweeps. To the best of our knowledge, this represents the first study, using in situ XAS, to resolve the synergistic catalytic mechanism of a bimetallic oxide. Strategies developed/described herein can provide a promising approach to unveil the reaction mechanism for other multimetallic electrocatalysts.
Electrocatalysis has been the cornerstone for enhancing energy efficiency, minimizing environmental impacts and carbon emissions, and enabling a more sustainable way of meeting global energy needs. Elucidating the structure and reaction mechanisms of electrocatalysts at electrode–electrolyte interfaces is fundamental for advancing renewable energy technologies, including fuel cells, water electrolyzers, CO2 reduction, and batteries, among others. One of the fundamental challenges in electrocatalysis is understanding how to activate and sustain electrocatalytic activity, under operating conditions, for extended time periods and with optimal activity and selectivity. Although traditional ex situ methods have provided a baseline understanding of heterogeneous (electro)catalysts, they cannot provide real-time interfacial structural and compositional changes under reaction conditions, which calls for the use of in situ/operando methods. Herein, we provide a selective review of in situ and operando characterizations, in particular, the use of operando synchrotron-based X-ray techniques and in situ atomic-scale scanning transmission electron microscopy (STEM) in liquid/gas phases to advance our understanding of electrode–electrolyte interfaces at macro- and microscopic levels, which dictate the charge transfer kinetics and overall reaction mechanisms. The use of scanning electrochemical microscopy (SECM) enables direct probing of the local activity of electrocatalysts at the nanometer scale. In addition, differential electrochemical mass spectrometry (DEMS) and the electrochemical quartz crystal balance (EQCM) enable the simultaneous identification of multiple reaction intermediates and products for mechanistic studies of electrocatalyst selectivity and durability. We anticipate that continuous advances of in situ/operando techniques and probes will continue to make significant contributions to establishing structure/composition-reactivity correlations of electrocatalysts at unprecedented atomic-scale and molecular levels under realistic, real-time reaction conditions.
Ordered intermetallic nanoparticles are promising electrocatalysts with enhanced activity and durability for the oxygen-reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). The ordered phase is generally identified based on the existence of superlattice ordering peaks in powder X-ray diffraction (PXRD). However, after employing a widely used postsynthesis annealing treatment, we have found that claims of “ordered” catalysts were possibly/likely mixed phases of ordered intermetallics and disordered solid solutions. Here, we employed in situ heating, synchrotron-based, X-ray diffraction to quantitatively investigate the impact of a variety of annealing conditions on the degree of ordering of large ensembles of Pt3Co nanoparticles. Monte Carlo simulations suggest that Pt3Co nanoparticles have a lower order–disorder phase transition (ODPT) temperature relative to the bulk counterpart. Furthermore, we employed microscopic-level in situ heating electron microscopy to directly visualize the morphological changes and the formation of both fully and partially ordered nanoparticles at the atomic scale. In general, a higher degree of ordering leads to more active and durable electrocatalysts. The annealed Pt3Co/C with an optimal degree of ordering exhibited significantly enhanced durability, relative to the disordered counterpart, in practical membrane electrode assembly (MEA) measurements. The results highlight the importance of understanding the annealing process to maximize the degree of ordering in intermetallics to optimize electrocatalytic activity.
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