Confined microemulsions: pore diameter induced change of the phase behavior.

In the present work, the temperature-dependent phase behavior of a C10E4 based microemulsion is studied in different meso-macroporous glasses, as a function of their pore diameter. The phase behavior in these pores is investigated by small-angle X-ray scattering (SAXS). The crucial parameter we discuss based on the SAXS results is the domain size of the bicontinuous phase. Using a simplified model to fit the scattering data, we can observe the microemulsion inside the pores. These experiments reveal a temperature-dependent change in domain sizes of the bicontinuous microemulsion only for large pores.

Scale-Up of PTFE-Based Gas Diffusion Electrodes Using an Electrolyte-Integrated Polymer-Coated Current Collector Approach.

Nonconductive porous polymer substrates, such as PTFE, have been pivotal in the fabrication of stable and high-performing gas diffusion electrodes (GDEs) for the reduction of CO2/CO in small scale electrolyzers; however, the scale-up of polymer-based GDEs without performance penalties to technologically more relevant electrode sizes has remained elusive. This work reports on a new current collector concept that enables the scale-up of PTFE-based GDEs from 5 to 100 cm2 and beyond. The present approach builds on a multifunctional current collector concept that enables multipoint front-contacting of thin catalyst coatings, which mitigates performance losses even for high resistivity cathodes. Our improved current collector design concomitantly incorporates a flow-field functionality in a monopolar plate configuration, keeping electrolyte gaps small for increased performance. Experiments with 100 cm2 cathodes were conducted in a one-gap alkaline AEM and acid CEM system. Our design represents an important step forward in the development of larger-size CO2 electrolyzers.

Electrochemical CO2 Activation and Valorization on Metallic Copper and Carbon-Embedded N-Coordinated Single Metal MNC Catalysts.

The electrochemical reductive valorization of CO2, referred to as the CO2RR, is an emerging approach for the conversion of CO2-containing feeds into valuable carbonaceous fuels and chemicals, with potential contributions to carbon capture and use (CCU) for reducing greenhouse gas emissions. Copper surfaces and graphene-embedded, N-coordinated single metal atom (MNC) catalysts exhibit distinctive reactivity, attracting attention as efficient electrocatalysts for CO2RR. This review offers a comparative analysis of CO2RR on copper surfaces and MNC catalysts, highlighting their unique characteristics in terms of CO2 activation, C1/C2(+) product formation, and the competing hydrogen evolution pathway. The assessment underscores the significance of understanding structure-activity relationships to optimize catalyst design for efficient and selective CO2RR. Examining detailed reaction mechanisms and structure-selectivity patterns, the analysis explores recent insights into changes in the chemical catalyst states, atomic motif rearrangements, and fractal agglomeration, providing essential kinetic information from advanced in/ex situ microscopy/spectroscopy techniques. At the end, this review addresses future challenges and solutions related to today's disconnect between our current molecular understanding of structure-activity-selectivity relations in CO2RR and the relevant factors controlling the performance of CO2 electrolyzers over longer times, with larger electrode sizes, and at higher current densities.

Facilitating alkaline hydrogen evolution reaction on the hetero-interfaced Ru/RuO2 through Pt single atoms doping.

Exploring an active and cost-effective electrocatalyst alternative to carbon-supported platinum nanoparticles for alkaline hydrogen evolution reaction (HER) have remained elusive to date. Here, we report a catalyst based on platinum single atoms (SAs) doped into the hetero-interfaced Ru/RuO2 support (referred to as Pt-Ru/RuO2), which features a low HER overpotential, an excellent stability and a distinctly enhanced cost-based activity compared to commercial Pt/C and Ru/C in 1 M KOH. Advanced physico-chemical characterizations disclose that the sluggish water dissociation is accelerated by RuO2 while Pt SAs and the metallic Ru facilitate the subsequent H* combination. Theoretical calculations correlate with the experimental findings. Furthermore, Pt-Ru/RuO2 only requires 1.90 V to reach 1 A cm-2 and delivers a high price activity in the anion exchange membrane water electrolyzer, outperforming the benchmark Pt/C. This research offers a feasible guidance for developing the noble metal-based catalysts with high performance and low cost toward practical H2 production.

Unraveling the synergistic effects of Cu-Ag tandem catalysts during electrochemical CO2 reduction using nanofocused X-ray probes.

Controlling the selectivity of the electrocatalytic reduction of carbon dioxide into value-added chemicals continues to be a major challenge. Bulk and surface lattice strain in nanostructured electrocatalysts affect catalytic activity and selectivity. Here, we unravel the complex dynamics of synergistic lattice strain and stability effects of Cu-Ag tandem catalysts through a previously unexplored combination of in situ nanofocused X-ray absorption spectroscopy and Bragg coherent diffraction imaging. Three-dimensional strain maps reveal the lattice dynamics inside individual nanoparticles as a function of applied potential and product yields. Dynamic relations between strain, redox state, catalytic activity and selectivity are derived. Moderate Ag contents effectively reduce the competing evolution of H2 and, concomitantly, lead to an enhanced corrosion stability. Findings from this study evidence the power of advanced nanofocused spectroscopy techniques to provide new insights into the chemistry and structure of nanostructured catalysts.

Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods.

Mononuclear Fe ions ligated by nitrogen (FeNx) dispersed on nitrogen-doped carbon (Fe-N-C) serve as active centers for electrocatalytic O2 reduction and thermocatalytic aerobic oxidations. Despite their promise as replacements for precious metals in a variety of practical applications, such as fuel cells, the discovery of new Fe-N-C catalysts has relied primarily on empirical approaches. In this context, the development of quantitative structure-reactivity relationships and benchmarking of catalysts prepared by different synthetic routes and by different laboratories would be facilitated by the broader adoption of methods to quantify atomically dispersed FeNx active centers. In this study, we develop a kinetic probe reaction method that uses the aerobic oxidation of a model hydroquinone substrate to quantify the density of FeNx centers in Fe-N-C catalysts. The kinetic method is compared with low-temperature Mössbauer spectroscopy, CO pulse chemisorption, and electrochemical reductive stripping of NO derived from NO2- on a suite of Fe-N-C catalysts prepared by diverse routes and featuring either the exclusive presence of Fe as FeNx sites or the coexistence of aggregated Fe species in addition to FeNx. The FeNx site densities derived from the kinetic method correlate well with those obtained from CO pulse chemisorption and Mössbauer spectroscopy. The broad survey of Fe-N-C materials also reveals the presence of outliers and challenges associated with each site quantification approach. The kinetic method developed here does not require pretreatments that may alter active-site distributions or specialized equipment beyond reaction vessels and standard analytical instrumentation.

Defect-Promoted Ni-Based Layer Double Hydroxides with Enhanced Deprotonation Capability for Efficient Biomass Electrooxidation.

Ni-based hydroxides are promising electrocatalysts for biomass oxidation reactions, supplanting the oxygen evolution reaction (OER) due to lower overpotentials while producing value-added chemicals. The identification and subsequent engineering of their catalytically active sites are essential to facilitate these anodic reactions. Herein, the proportional relationship between catalysts' deprotonation propensity and Faradic efficiency of 5-hydroxymethylfurfural (5-HMF)-to-2,5 furandicarboxylic acid (FDCA, FEFDCA ) is revealed by thorough density functional theory (DFT) simulations and atomic-scale characterizations, including in situ synchrotron diffraction and spectroscopy methods. The deprotonation capability of ultrathin layer-double hydroxides (UT-LDHs) is regulated by tuning the covalency of metal (M)-oxygen (O) motifs through defect site engineering and selection of M3+ co-chemistry. NiMn UT-LDHs show an ultrahigh FEFDCA of 99% at 1.37 V versus reversible hydrogen electrode (RHE) and retain a high FEFDCA of 92.7% in the OER-operating window at 1.52 V, about 2× that of NiFe UT-LDHs (49.5%) at 1.52 V. Ni-O and Mn-O motifs function as dual active sites for HMF electrooxidation, where the continuous deprotonation of Mn-OH sites plays a dominant role in achieving high selectivity while suppressing OER at high potentials. The results showcase a universal concept of modulating competing anodic reactions in aqueous biomass electrolysis by electronically engineering the deprotonation behavior of metal hydroxides, anticipated to be translatable across various biomass substrates.

Electrochemical carbonyl reduction on single-site M-N-C catalysts.

Electrochemical conversion of organic compounds holds promise for advancing sustainable synthesis and catalysis. This study explored electrochemical carbonyl hydrogenation on single-site M-N-C (Metal Nitrogen-doped Carbon) catalysts using formaldehyde, acetaldehyde, and acetone as model reactants. We strive to correlate and understand the selectivity dependence on the nature of the metal centers. Density Functional Theory calculations revealed similar binding energetics for carbonyl groups through oxygen-down or carbon-down adsorption due to oxygen and carbon scaling. Fe-N-C exhibited specific oxyphilicity and could selectively reduce aldehydes to hydrocarbons. By contrast, the carbophilic Co-N-C selectively converted acetaldehyde and acetone to ethanol and 2-propanol, respectively. We claim that the oxyphilicity of the active sites and consequent adsorption geometry (oxygen-down vs. carbon-down) are crucial in controlling product selectivity. These findings offer mechanistic insights into electrochemical carbonyl hydrogenation and can guide the development of efficient and sustainable electrocatalytic valorization of biomass-derived compounds.

A CO2 electrolyzer tandem cell system for CO2-CO co-feed valorization in a Ni-N-C/Cu-catalyzed reaction cascade.

Coupled tandem electrolyzer concepts have been predicted to offer kinetic benefits to sluggish catalytic reactions thanks to their flexibility of reaction environments in each cell. Here we design, assemble, test, and analyze the first complete low-temperature, neutral-pH, cathode precious metal-free tandem CO2 electrolyzer cell chain. The tandem system couples an Ag-free CO2-to-CO2/CO electrolyzer (cell-1) to a CO2/CO-to-C2+ product electrolyzer (cell-2). Cell-1 and cell-2 incorporate selective Ni-N-C-based and Cu-based Gas Diffusion Cathodes, respectively, and operate at sustainable neutral pH conditions. Using our tandem cell system, we report strongly enhanced rates for the production of ethylene (by 50%) and alcohols (by 100%) and a sharply increased C2+ energy efficiency (by 100%) at current densities of up to 700 mA cm-2 compared to the single CO2-to-C2+ electrolyzer cell system approach. This study demonstrates that coupled tandem electrolyzer cell systems can offer kinetic and practical energetic benefits over single-cell designs for the production of value-added C2+ chemicals and fuels directly from CO2 feeds without intermediate separation or purification.

Hydrogenation versus hydrogenolysis during alkaline electrochemical valorization of 5-hydroxymethylfurfural over oxide-derived Cu-bimetallics.

The electrochemical conversion of 5-Hydroxymethylfurfural, especially its reduction, is an attractive green production pathway for carbonaceous e-chemicals. We demonstrate the reduction of 5-Hydroxymethylfurfural to 5-Methylfurfurylalcohol under strongly alkaline reaction environments over oxide-derived Cu bimetallic electrocatalysts. We investigate whether and how the surface catalysis of the MOx phases tune the catalytic selectivity of oxide-derived Cu with respect to the 2-electron hydrogenation to 2.5-Bishydroxymethylfuran and the (2 + 2)-electron hydrogenation/hydrogenolysis to 5-Methylfurfurylalcohol. We provide evidence for a kinetic competition between the evolution of H2 and the 2-electron hydrogenolysis of 2.5-Bishydroxymethylfuran to 5-Methylfurfurylalcohol and discuss its mechanistic implications. Finally, we demonstrate that the ability to conduct 5-Hydroxymethylfurfural reduction to 5-Methylfurfurylalcohol in alkaline conditions over oxide-derived Cu/MOx Cu foam electrodes enable an efficiently operating alkaline exchange membranes electrolyzer, in which the cathodic 5-Hydroxymethylfurfural valorization is coupled to either alkaline oxygen evolution anode or to oxidative 5-Hydroxymethylfurfural valorization.

Structural and Reactivity Effects of Secondary Metal Doping into Iron-Nitrogen-Carbon Catalysts for Oxygen Electroreduction.

While improved activity was recently reported for bimetallic iron-metal-nitrogen-carbon (FeMNC) catalysts for the oxygen reduction reaction (ORR) in acid medium, the nature of active sites and interactions between the two metals are poorly understood. Here, FeSnNC and FeCoNC catalysts were structurally and catalytically compared to their parent FeNC and SnNC catalysts. While CO cryo-chemisorption revealed a twice lower site density of M-Nx sites for FeSnNC and FeCoNC relative to FeNC and SnNC, the mass activity of both bimetallic catalysts is 50-100% higher than that of FeNC due to a larger turnover frequency in the bimetallic catalysts. Electron microscopy and X-ray absorption spectroscopy identified the coexistence of Fe-Nx and Sn-Nx or Co-Nx sites, while no evidence was found for binuclear Fe-M-Nx sites. 57Fe Mössbauer spectroscopy revealed that the bimetallic catalysts feature a higher D1/D2 ratio of the spectral signatures assigned to two distinct Fe-Nx sites, relative to the FeNC parent catalyst. Thus, the addition of the secondary metal favored the formation of D1 sites, associated with the higher turnover frequency.

Degradation of Phenol via an Advanced Oxidation Process (AOP) with Immobilized Commercial Titanium Dioxide (TiO2) Photocatalysts.

Four commercial titanium dioxide (TiO2) photocatalysts, namely P25, P90, PC105, and PC500, were immobilized onto steel plates using a sol-gel binder and investigated for phenol degradation under 365 nm UV-LED irradiation. High-performance liquid chromatography (HPLC) and total organic carbon (TOC) analyses were performed to study the impact of three types of oxygen sources (air, dispersed synthetic air, and hydrogen peroxide) on the photocatalytic performance. The photocatalyst films were stable and there were significant differences in their performance. The best result was obtained with the P90/UV/H2O2 system with 100% degradation and about 70% mineralization within 3 h of irradiation. The operating conditions varied, showing that water quality is crucial for the performance. A wastewater treatment plant was developed based on the lab-scale results and water treatment costs were estimated for two cases of irradiation: UV-LED (about 600 EUR/m3) and sunlight (about 60 EUR/m3). The data show the high potential of immobilized photocatalysts for pollutant degradation under advanced oxidation process (AOP) conditions, but there is still a need for optimization to further reduce treatment costs.

Electroreduction of CO2 on Au(310)@Cu High-index Facets.

The chemical selectivity and faradaic efficiency of high-index Cu facets for the CO2 reduction reaction (CO2 RR) is investigated. More specifically, shape-controlled nanoparticles enclosed by Cu {hk0} facets are fabricated using Cu multilayer deposition at three distinct layer thicknesses on the surface facets of Au truncated ditetragonal nanoprisms (Au DTPs). Au DTPs are shapes enclosed by 12 high-index {310} facets. Facet angle analysis confirms DTP geometry. Elemental mapping analysis shows Cu surface layers are uniformly distributed on the Au {310} facets of the DTPs. The 7 nm Au@Cu DTPs high-index {hk0} facets exhibit a CH4 : CO product ratio of almost 10 : 1 compared to a 1 : 1 ratio for the reference 7 nm Au@Cu nanoparticles (NPs). Operando Fourier transform infrared spectroscopy spectra disclose reactive adsorbed *CO as the main intermediate, whereas CO stripping experiments reveal the high-index facets enhance the *CO formation followed by rapid desorption or hydrogenation.

Iridium single atoms incorporated in Co3O4 efficiently catalyze the oxygen evolution in acidic conditions.

Designing active and stable electrocatalysts with economic efficiency for acidic oxygen evolution reaction is essential for developing proton exchange membrane water electrolyzers. Herein, we report on a cobalt oxide incorporated with iridium single atoms (Ir-Co3O4), prepared by a mechanochemical approach. Operando X-ray absorption spectroscopy reveals that Ir atoms are partially oxidized to active Ir>4+ during the reaction, meanwhile Ir and Co atoms with their bridged electrophilic O ligands acting as active sites, are jointly responsible for the enhanced performance. Theoretical calculations further disclose the isolated Ir atoms can effectively boost the electronic conductivity and optimize the energy barrier. As a result, Ir-Co3O4 exhibits significantly higher mass activity and turnover frequency than those of benchmark IrO2 in acidic conditions. Moreover, the catalyst preparation can be easily scaled up to gram-level per batch. The present approach highlights the concept of constructing single noble metal atoms incorporated cost-effective metal oxides catalysts for practical applications.

Mo-Incorporated Magnetite Fe3 O4 Featuring Cationic Vacancies Enabling Fast Lithium Intercalation for Batteries.

Transition metal oxides (TMOs) as high-capacity electrodes have several drawbacks owing to their inherent poor electronic conductivity and structural instability during the multi-electron conversion reaction process. In this study, the authors use an intrinsic high-valent cation substitution approach to stabilize cation-deficient magnetite (Fe3 O4 ) and overcome the abovementioned issues. Herein, 5 at% of Mo4+ -ions are incorporated into the spinel structure to substitute octahedral Fe3+ -ions, featuring ≈1.7 at% cationic vacancies in the octahedral sites. This defective Fe2.93 ▫0.017 Mo0.053 O4 electrode shows significant improvements in the mitigation of capacity fade and the promotion of rate performance as compared to the pristine Fe3 O4 . Furthermore, physical-electrochemical analyses and theoretical calculations are performed to investigate the underlying mechanisms. In Fe2.93 ▫0.017 Mo0.053 O4 , the cationic vacancies provide active sites for storing Li+ and vacancy-mediated Li+ migration paths with lower energy barriers. The enlarged lattice and improved electronic conductivity induced by larger doped-Mo4+ yield this defective oxide capable of fast lithium intercalation. This is confirmed by a combined characterization including electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT) and density functional theory (DFT) calculation. This study provides a valuable strategy of vacancy-mediated reaction to intrinsically modulate the defective structure in TMOs for high-performance lithium-ion batteries.

On the electrocatalytical oxygen reduction reaction activity and stability of quaternary RhMo-doped PtNi/C octahedral nanocrystals.

Recently proposed bimetallic octahedral Pt-Ni electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cell (PEMFC) cathodes suffer from particle instabilities in the form of Ni corrosion and shape degradation. Advanced trimetallic Pt-based electrocatalysts have contributed to their catalytic performance and stability. In this work, we propose and analyse a novel quaternary octahedral (oh-)Pt nanoalloy concept with two distinct metals serving as stabilizing surface dopants. An efficient solvothermal one-pot strategy was developed for the preparation of shape-controlled oh-PtNi catalysts doped with Rh and Mo in its surface. The as-prepared quaternary octahedral PtNi(RhMo) catalysts showed exceptionally high ORR performance accompanied by improved activity and shape integrity after stability tests compared to previously reported bi- and tri-metallic systems. Synthesis, performance characteristics and degradation behaviour are investigated targeting deeper understanding for catalyst system improvement strategies. A number of different operando and on-line analysis techniques were employed to monitor the structural and elemental evolution, including identical location scanning transmission electron microscopy and energy dispersive X-ray analysis (IL-STEM-EDX), operando wide angle X-ray spectroscopy (WAXS), and on-line scanning flow cell inductively coupled plasma mass spectrometry (SFC-ICP-MS). Our studies show that doping PtNi octahedral catalysts with small amounts of Rh and Mo suppresses detrimental Pt diffusion and thus offers an attractive new family of shaped Pt alloy catalysts for deployment in PEMFC cathode layers.

Low-Pt NiNC-Supported PtNi Nanoalloy Oxygen Reduction Reaction Electrocatalysts-In Situ Tracking of the Atomic Alloying Process.

We report and analyze a synthetic strategy toward low-Pt platinum-nickel (Pt-Ni) alloy nanoparticle (NP) cathode catalysts for the catalytic electroreduction of molecular oxygen to water. The synthesis involves the pyrolysis and leaching of Ni-organic polymers, subsequent Pt NP deposition, followed by thermal alloying, resulting in single Ni atom site (NiNC)-supported PtNi alloy NPs at low Pt weight loadings of only 3-5 wt %. Despite low Pt weight loading, the catalysts exhibit more favorable Pt-mass activities compared to conventional 20-30 wt % benchmark PtNi catalysts. Using in situ microscopic techniques, we track and unravel the key stages of the PtNi alloy formation process directly at the atomic scale. Surprisingly, we find that carbon-encapsulated metallic Ni@C structures, rather than NiNx sites, act as the Ni source during alloy formation. Our materials concepts offer a pathway to further decrease the overall Pt content in hydrogen fuel cell cathodes.

Kinetic Diagnostics and Synthetic Design of Platinum Group Metal-Free Electrocatalysts for the Oxygen Reduction Reaction Using Reactivity Maps and Site Utilization Descriptors.

The experimental development of catalytically ever-more active platinum group metal (PGM)-free materials for the oxygen reduction reaction (ORR) at fuel cell cathodes has been until recently a rather empirical iteration of synthesis and testing. Here, we present how kinetic reactivity maps based on kinetic descriptors of PGM-free single-metal-site ORR electrocatalysts can help to better understand the origin of catalytic reactivity and help to derive rational synthetic guidelines toward improved catalysts. Key in our analysis are the catalytic surface site density (SD) and the catalytic turnover frequency (TOF) in their role as controlling kinetic parameters for the ORR reactivity of PGM-free nitrogen-coordinated single-metal M-site carbon (MNC) catalysts. SD-TOF plots establish two-dimensional reactivity maps. We also consider the ratio between SD and the total number of single-metal sites in the bulk, referred to as the site utilization factor, which we propose as another guiding parameter for optimizing the synthesis of MNC catalysts. Exemplified by two sets of FeNC, CoNC, and SnNC catalysts prepared using two distinctly different N- and C-precursor material classes (Zn-based zeolitic imidazolate frameworks and covalent polyaniline), we comparatively diagnose the intrinsic kinetic ORR parameters as well as structural, morphological, and chemical properties. From there, we derive and discuss possible synthetic guidelines for further improvements. Our approach can be extended to other families of catalysts and may involve kinetic performance data of idealized liquid-electrolyte cells as well as gas diffusion layer-type flow cells.