CO Cryo-sorption as a Surface-sensitive Spectroscopic Probe of the Active Site Density of Single-atom Catalysts.

Quantifying the number of active sites is a crucial aspect in the performance evaluation of single metal-atom electrocatalysts. A possible realization is using adsorbing gas molecules that selectively bind to the single-atom transition metal and then probing their surface density using spectroscopic tools. Herein, using in situ X-ray photoelectron (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy, we detect adsorbed CO gas molecules on a FeNC oxygen reduction single atom catalyst.

Hierarchical Porous FeC@Fe-N-C Catalysts from Tannin-Fe(III) Complexes for Efficient Oxygen Reduction.

The rational design of metal-nitrogen-doped carbons (M-N-C) from available and cost-effective sources featuring high electrocatalytic performance and stability is attractive for the development of viable low-temperature fuel cells. Herein, mimosa tannin, an abundant polyphenol easily extracted from the Mimosa plant, is used as a natural carbon source to produce a tannin-Fe(III) coordination complex. This process is assisted by Pluronic F127, which acts as both a surfactant and a promoter of Fe-N active sites.

Exploring Spin Distribution and Electronic Properties in FeN-Graphene Catalysts with Edge Terminations.

Understanding the spin distribution in FeN-doped graphene nanoribbons with zigzag and armchair terminations is crucial for tuning the electronic properties of graphene-supported non-platinum catalysts. Since the spin-polarized carbon and iron electronic states may act together to change the electronic properties of the doped graphene, we provide in this work a systematic evaluation using a periodic density-functional theory-based method of the variation of spin-moment distribution and electronic properties with the position and orientation of the FeN defects, and the edge terminations of the graphene nanoribbons. Antiferromagnetic and ferromagnetic spin ordering of the zigzag edges were considered.

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 (FeN) dispersed on nitrogen-doped carbon (Fe-N-C) serve as active centers for electrocatalytic O 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 FeN active centers.

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.

Review on the Degradation Mechanisms of Metal-N-C Catalysts for the Oxygen Reduction Reaction in Acid Electrolyte: Current Understanding and Mitigation Approaches.

One bottleneck hampering the widespread use of fuel cell vehicles, in particular of proton exchange membrane fuel cells (PEMFCs), is the high cost of the cathode where the oxygen reduction reaction (ORR) occurs, due to the current need of precious metals to catalyze this reaction. Electrochemists tackle this issue in the short/medium term by developing catalysts with improved utilization or efficiency of platinum, and in the longer term, by developing catalysts based on Earth-abundant elements. Considerable progress has been achieved in the initial performance of Metal-nitrogen-carbon (Metal-N-C) catalysts for the ORR, especially with Fe-N-C materials.

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-N 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.

Spectroscopic Analysis of Axial Oxygen-Coordinated Single-Sn-Atom Sites for Electrochemical CO Reduction.

Sn-based materials have been demonstrated as promising catalysts for the selective electrochemical CO reduction reaction (CORR). However, the detailed structures of catalytic intermediates and the key surface species remain to be identified. In this work, a series of single-Sn-atom catalysts with well-defined structures is developed as model systems to explore their electrochemical reactivity toward CORR.

Doped Graphene To Mimic the Bacterial NADH Oxidase for One-Step NAD Supplementation in Mammals.

Nicotinamide adenine dinucleotide (NAD) is a critical regulator of metabolic networks, and declining levels of its oxidized form, NAD, are closely associated with numerous diseases. While supplementing cells with precursors needed for NAD synthesis has shown poor efficacy in combatting NAD decline, an alternative strategy is the development of synthetic materials that catalyze the oxidation of NADH into NAD, thereby taking over the natural role of the NADH oxidase (NOX) present in bacteria. Herein, we discovered that metal-nitrogen-doped graphene (MNGR) materials can catalyze the oxidation of NADH into NAD.

Oxygen Reduction Reaction in Alkaline Media Causes Iron Leaching from Fe-N-C Electrocatalysts.

The electrochemical activity of modern Fe-N-C electrocatalysts in alkaline media is on par with that of platinum. For successful application in fuel cells (FCs), however, also high durability and longevity must be demonstrated. Currently, a limited understanding of degradation pathways, especially under operando conditions, hinders the design and synthesis of simultaneously active and stable Fe-N-C electrocatalysts.

What is Next in Anion-Exchange Membrane Water Electrolyzers? Bottlenecks, Benefits, and Future.

As highlighted by the recent roadmaps from the European Union and the United States, water electrolysis is the most valuable high-intensity technology for producing green hydrogen. Currently, two commercial low-temperature water electrolyzer technologies exist: alkaline water electrolyzer (A-WE) and proton-exchange membrane water electrolyzer (PEM-WE). However, both have major drawbacks.

Quantification of Active Site Density and Turnover Frequency: From Single-Atom Metal to Nanoparticle Electrocatalysts.

Single-atom catalysts (SACs) featuring atomically dispersed metal cations covalently embedded in a carbon matrix show significant potential to achieve high catalytic performance in various electrocatalytic reactions. Although considerable advances have been achieved in their syntheses and electrochemical applications, further development and fundamental understanding are limited by a lack of strategies that can allow the quantitative analyses of their intrinsic catalytic characteristics, that is, active site density (SD) and turnover frequency (TOF). Here we show an SD quantification method using a cyanide anion as a probe molecule.

Chemical vapour deposition of Fe-N-C oxygen reduction catalysts with full utilization of dense Fe-N sites.

Replacing scarce and expensive platinum (Pt) with metal-nitrogen-carbon (M-N-C) catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells has largely been impeded by the low oxygen reduction reaction activity of M-N-C due to low active site density and site utilization. Herein, we overcome these limits by implementing chemical vapour deposition to synthesize Fe-N-C by flowing iron chloride vapour over a Zn-N-C substrate at 750 °C, leading to high-temperature trans-metalation of Zn-N sites into Fe-N sites. Characterization by multiple techniques shows that all Fe-N sites formed via this approach are gas-phase and electrochemically accessible.

Selective electrochemical reduction of nitric oxide to hydroxylamine by atomically dispersed iron catalyst.

Electrocatalytic conversion of nitrogen oxides to value-added chemicals is a promising strategy for mitigating the human-caused unbalance of the global nitrogen-cycle, but controlling product selectivity remains a great challenge. Here we show iron-nitrogen-doped carbon as an efficient and durable electrocatalyst for selective nitric oxide reduction into hydroxylamine. Using in operando spectroscopic techniques, the catalytic site is identified as isolated ferrous moieties, at which the rate for hydroxylamine production increases in a super-Nernstian way upon pH decrease.

Potential-Induced Spin Changes in Fe/N/C Electrocatalysts Assessed by In Situ X-ray Emission Spectroscopy.

The commercial success of the electrochemical energy conversion technologies required for the decarbonization of the energy sector requires the replacement of the noble metal-based electrocatalysts currently used in (co-)electrolyzers and fuel cells with inexpensive, platinum-group metal-free analogs. Among these, Fe/N/C-type catalysts display promising performances for the reduction of O or CO , but their insufficient activity and stability jeopardize their implementation in such devices. To circumvent these issues, a better understanding of the local geometric and electronic structure of their catalytic active sites under reaction conditions is needed.

Narrow resection margins are not associated with mortality or recurrence in patients with Merkel cell carcinoma: A retrospective study.

Background: Wide local excision constitutes the standard of care for Merkel cell carcinoma, but the optimal margin width remains controversial.

Objectives: To assess whether narrow margins (0.5-1 cm) were associated with outcome.

Engineering Fe-N Doped Graphene to Mimic Biological Functions of NADPH Oxidase in Cells.

NADPH oxidase (NOX) as a transmembrane enzyme complex controls the generation of superoxide that plays important roles in immune signaling pathway. NOX inactivation may elicit immunodeficiency and cause chronic granulomatous disease (CGD). Biocompatible synthetic materials with NOX-like activities would therefore be interesting as curative and/or preventive approaches in case of NOX deficiency.

P-block single-metal-site tin/nitrogen-doped carbon fuel cell cathode catalyst for oxygen reduction reaction.

This contribution reports the discovery and analysis of a p-block Sn-based catalyst for the electroreduction of molecular oxygen in acidic conditions at fuel cell cathodes; the catalyst is free of platinum-group metals and contains single-metal-atom actives sites coordinated by nitrogen. The prepared SnNC catalysts meet and exceed state-of-the-art FeNC catalysts in terms of intrinsic catalytic turn-over frequency and hydrogen-air fuel cell power density. The SnNC-NH catalysts displayed a 40-50% higher current density than FeNC-NH at cell voltages below 0.

Evolution Pathway from Iron Compounds to Fe(II)-N Sites through Gas-Phase Iron during Pyrolysis.

Pyrolysis is indispensable for synthesizing highly active Fe-N-C catalysts for the oxygen reduction reaction (ORR) in acid, but how Fe, N, and C precursors transform to ORR-active sites during pyrolysis remains unclear. This knowledge gap obscures the connections between the input precursors and the output products, clouding the pathway toward Fe-N-C catalyst improvement. Herein, we unravel the evolution pathway of precursors to ORR-active catalyst comprised exclusively of single-atom Fe(II)-N sites via in-temperature X-ray absorption spectroscopy.