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One of the grand challenges facing electrochemistry is to directly resolve the complex nature of (electro)catalyst active sites and capture real-time “movies” of reaction dynamics, i.e. “watching chemistry in action”. The need for such fundamental understanding has stimulated the development of operando/in situ methods, which have greatly enhanced our ability to identify activity descriptors of electrocatalysts and establish structure–property relationships of energy materials. This review summarizes the frontiers of operando electrochemical liquid-cell scanning transmission electron microscopy and correlative synchrotron X-ray methods, which are complementary tools to comprehensively investigate reaction dynamics across multiple spatiotemporal scales. In an effort to encourage greater adoption of advanced operando methods by the general electrochemistry community, this review points out the need to benchmark electrochemistry in confined and heterogenous liquid environment with minimal beam-induced damage. We anticipate that multimodal operando methods will become indispensable for understanding interfacial reaction mechanisms for the broad chemistry and energy materials communities.

Advances in electrocatalysis research rely heavily on building a thorough mechanistic understanding of catalyst active sites under realistic operating conditions. Only recently have techniques emerged that enable sensitive spectroscopic data collection to distinguish catalytically relevant surface sites from the underlying bulk material under applied potential in the presence of an electrolyte layer. Here, we demonstrate that operando high-energy-resolution fluorescence detected X-ray absorption spectroscopy (HERFD-XAS) is a powerful spectroscopic method which offers critical surface chemistry insights in CO2 electroreduction with sub-electronvolt energy resolution using hard X-rays. Combined with the high surface area-to-volume ratio of 5 nm copper nanoparticles, operando HERFD-XAS allows us to observe with clear evidence the breaking of chemical bonds between the ligands and the Cu surface as part of the ligand desorption process occurring under electrochemical potentials relevant for the CO2 reduction reaction (CO2RR). In addition, the dynamic evolution of oxidation state and coordination number throughout the operation of the nanocatalyst was continuously tracked. With these results in hand, undercoordinated metallic copper nanograins are proposed to be the real active sites in the CO2RR. This work emphasizes the importance of HERFD-XAS compared to routine XAS in catalyst characterization and mechanism exploration, especially in the complicated electrochemical CO2RR.

Carbon dioxide electroreduction facilitates the sustainable synthesis of fuels and chemicals1. Although Cu enables CO2-to-multicarbon product (C2+) conversion, the nature of the active sites under operating conditions remains elusive2. Importantly, identifying active sites of high-performance Cu nanocatalysts necessitates nanoscale, time-resolved operando techniques3-5. 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 complete oxidation to single-crystal Cu2O nanocubes following post-electrolysis air exposure. Operando analytical and four-dimensional electrochemical liquid-cell scanning transmission electron microscopy shows the presence of metallic Cu nanograins under CO2 reduction conditions. Correlated high-energy-resolution time-resolved X-ray spectroscopy suggests that metallic Cu, rich in nanograin boundaries, supports undercoordinated active sites for C-C coupling. Quantitative structure-activity correlation shows that a higher fraction of metallic Cu nanograins leads to higher C2+ selectivity. A 7 nm Cu nanoparticle ensemble, with a unity fraction of active Cu nanograins, exhibits sixfold higher C2+ selectivity than the 18 nm counterpart with one-third of active Cu nanograins. The correlation of multimodal operando techniques serves as a powerful platform to advance our fundamental understanding of the complex structural evolution of nanocatalysts under electrochemical conditions.

X-ray crystallography at X-ray free-electron laser sources is a powerful method for studying macromolecules at biologically relevant temperatures. Moreover, when combined with complementary techniques like X-ray emission spectroscopy, both global structures and chemical properties of metalloenzymes can be obtained concurrently, providing insights into the interplay between the protein structure and dynamics and the chemistry at an active site. The implementation of such a multimodal approach can be compromised by conflicting requirements to optimize each individual method. In particular, the method used for sample delivery greatly affects the data quality. We present here a robust way of delivering controlled sample amounts on demand using acoustic droplet ejection coupled with a conveyor belt drive that is optimized for crystallography and spectroscopy measurements of photochemical and chemical reactions over a wide range of time scales. Studies with photosystem II, the phytochrome photoreceptor, and ribonucleotide reductase R2 illustrate the power and versatility of this method.

A series of vanadium compounds was studied by K-edge X-ray absorption (XAS) and K[Formula: see text] X-ray emission spectroscopies (XES). Qualitative trends within the datasets, as well as comparisons between the XAS and XES data, illustrate the information content of both methods. The complementary nature of the chemical insight highlights the success of this dual-technique approach in characterizing both the structural and electronic properties of vanadium sites. In particular, and in contrast to XAS or extended X-ray absorption fine structure (EXAFS), we demonstrate that valence-to-core XES is capable of differentiating between ligating atoms with the same identity but different bonding character. Finally, density functional theory (DFT) and time-dependent DFT calculations enable a more detailed, quantitative interpretation of the data. We also establish correction factors for the computational protocols through calibration to experiment. These hard X-ray methods can probe vanadium ions in any oxidation or spin state, and can readily be applied to sample environments ranging from solid-phase catalysts to biological samples in frozen solution. Thus, the combined XAS and XES approach, coupled with DFT calculations, provides a robust tool for the study of vanadium atoms in bioinorganic chemistry.

Carbon dioxide electroreduction facilitates the sustainable synthesis of fuels and chemicals1. Although Cu enables CO2-to-multicarbon product (C2+) conversion, the nature of the active sites under operating conditions remains elusive2. Importantly, identifying active sites of high-performance Cu nanocatalysts necessitates nanoscale, time-resolved operando techniques3–5. 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 complete oxidation to single-crystal Cu2O nanocubes following post-electrolysis air exposure. Operando analytical and four-dimensional electrochemical liquid-cell scanning transmission electron microscopy shows the presence of metallic Cu nanograins under CO2 reduction conditions. Correlated high-energy-resolution time-resolved X-ray spectroscopy suggests that metallic Cu, rich in nanograin boundaries, supports undercoordinated active sites for C–C coupling. Quantitative structure–activity correlation shows that a higher fraction of metallic Cu nanograins leads to higher C2+ selectivity. A 7 nm Cu nanoparticle ensemble, with a unity fraction of active Cu nanograins, exhibits sixfold higher C2+ selectivity than the 18 nm counterpart with one-third of active Cu nanograins. The correlation of multimodal operando techniques serves as a powerful platform to advance our fundamental understanding of the complex structural evolution of nanocatalysts under electrochemical conditions.By investigation of structural dynamics during the life cycle of Cu nanocatalysts, correlation of multimodal operando techniques was found to serve as a powerful platform to advance understanding of their complex structural evolution. [ABSTRACT FROM AUTHOR]

A soluble acid invertase was extracted by mechanical disruption of mycelium of the psychrophile Monographella nivalis grown on sucrose in submerged culture. The crude preparation was stable to incubation at pH 6.2 for 1 h at temperatures up to 47 °C and was stable to handling at room temperature. Half of the initial activity was lost after 1 h at 52 °C and all activity was lost after 1 h at 57 °C. A single isoform with activity against sucrose was detected on both native PAGE and IEF activity gels, exhibiting an isoelectric point of pH 3.6. The activity bound tightly to Concanavalin A-sepharose and was not displaced by 500 mM α-methyl mannopyranosidase indicating the enzyme to be a mannose-containing glycoprotein. By gel filtration, the apparent Mr was determined at 195 kDa. The invertase was purified 106-fold by salt precipitation. The partially purified enzyme exhibited maximal activity at pH 4.2 and apparent Michaelis constants for sucrose of 1.2, 2.0 and 2.6 mM at 3, 9 and 15 °C. The activity increased exponentially with temperature in the range 7-55 °C. Q10 fell with increased temperature giving values of 1.96 between 5 and 15 °C and 1.60 between 40 and 50°C. Maximal activity was recorded at 55 °C. Arrhenius analysis of temperature data in the range 7-52 °C produced a continuous linear relationship. The activation energy for sucrose hydrolysis was 38.8 kJ mol-1. The thermal stability and thermal kinetic properties of the invertase were similar to those of invertases from mesophilic organisms. The invertase catalysed fructosyl transfer at 13% of the molar activity against sucrose when assayed under conditions analogous to those in culture. The major fructan products were neokestose, isokestose, kestose and an unidentified tetrasaccharide. Traces of larger fructans were also detected. The transient accumulation of fructan in cultures of M. nivalis can be explained as a side reaction of invertase activity. The enzymological and physiological data do not suggest a cryoprotective function for fructan during the growth of the fungus. [ABSTRACT FROM AUTHOR]

An asporogenous strain of the pink snow mould fungus, Monographella nivalis (Schaffnit) E. Müller, anamorph Gerlachia nivalis Ces. ex Sac.) W. Gams & E. Müller (Syn. Fusarium nivale Ces. ex Sacc.), grew at 5 °C on a defined salts medium plus vitamins and utilized a variety of simple and polymeric carbohydrates as the sole carbon and energy source. Mycelium was grown at temperatures between 3 and 15 °C in aerated submerged fermentation culture in chemically defined mediam plus sucrose. Optimum growth rates of 0.035-0.033 h-1 occurred between 9 and 12 °C. Growth in a simple medium showed that all biochemical and physiological processes necessary for growth were functional at 3 °C. The growth performance of the organism at low temperatures was no better than would be expected from extrapolation of mesophilic growth responses to temperature. The optimum growth temperature of 9-12 °C showed that some biochemical or physiological process was impaired above 12 °C. Uptake and incorporation of 35S-methionine by mycelium at different temperatures showed that general protein synthesis increased up to 25 °C, and hence was not responsible per se for the sensitivity to temperatures above 12 °C. Heat shock proteins were synthesized at the relatively low temperature of 25 °C, consistent with the low temperature optimum for growth. When grown with sucrose as the sole carbon source, the mycelium catalyzed the extracellular hydrolysis of sucrose, releasing glucose and fructose together with a small amount of fructan trisaccharides and a trace of tetra- and penta-saccharides. Fructan accumulation was transient, corresponding with maximal rates of sucrose hydrolysis. Most biomass formation occurred in the absence of fructan in the culture, hence fructan was not necessary for growth at low temperature and did not appear to function as a cryoprotectant. Invertase activity was mostly (60-70%) bound to mycelium; the remainder was free in the culture supernatant. The regulation of invertase expression appeared to be by sucrose-induction, rather than by end-product repression. Rates of sucrose hydrolysis in culture were temperature-sensitive and were markedly depressed above 12c, indicating inhibition of invertase formation. [ABSTRACT FROM AUTHOR]

The article provides information on a study focused on lithium-sulfur batteries, exploring the electrocatalytic mechanisms using a cobalt single-atom electrocatalyst through operando confocal Raman microscopy and x-ray absorption spectroscopy. The study reveals that Co-SAs/NC effectively accelerates lithium-sulfur reduction/oxidation reactions and transforms the stepwise mechanism of long-chain and intermediate-chain polysulfides into a concurrent pathway under electrocatalysis.

Discusses the distribution and activity of invertase in mature leaves of Lolium temulentum in relation to the anabolic and catabolic processes that occur in such tissues. Metabolism of sucrose in heterotophic epidermis and vasculature tissues; Changes in assimilate abundance; Patterns of gene expression; Metabolism of oligosaccharides based on sucrose.

Carbon dioxide 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 3-5 . 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 complete oxidation to single-crystal Cu 2 O nanocubes following post-electrolysis air exposure. Operando analytical and four-dimensional electrochemical liquid-cell scanning transmission electron microscopy shows the presence of metallic Cu nanograins under CO 2 reduction conditions. Correlated high-energy-resolution time-resolved X-ray spectroscopy suggests that metallic Cu, rich in nanograin boundaries, supports undercoordinated active sites for C-C coupling. Quantitative structure-activity correlation shows that 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 sixfold higher C 2+ selectivity than the 18 nm counterpart with one-third of active Cu nanograins. The correlation of multimodal operando techniques serves as a powerful platform to advance our fundamental understanding of the complex structural evolution of nanocatalysts under electrochemical conditions., (© 2023. The Author(s), under exclusive licence to Springer Nature Limited.)