Most cited article - PubMed ID 30811705
Mixed-Valence Single-Atom Catalyst Derived from Functionalized Graphene
The global transition to sustainable energy production revolves around innovations in electrocatalysis, the cornerstone of energy conversion technologies. Over the years, catalysts have evolved from bulk materials to nanoparticles (NPs) and nanoclusters (NCs), culminating in single-atom catalysts (SACs), which represent the peak of catalyst engineering. SACs have revolutionized electrocatalytic processes by maximizing atom efficiency and offering tunable electronic properties, lowering the energy barrier associated with the absorption and desorption of key reaction intermediates, thus promoting specific reaction pathways. This review delves into the synthesis, characterization, and theoretical modeling of SACs, offering a comprehensive analysis of state-of-the-art methodologies. It highlights recent breakthroughs in diverse electrocatalytic reactions, including the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting, the oxygen reduction reaction (ORR) for Zn-air batteries and fuel cells, the CO2 reduction reaction (CO2RR), and green ammonia synthesis. The discussion emphasizes the unique mechanisms that drive the exceptional performance of SACs, shedding light on their unparalleled activity, selectivity, and stability. By integrating experimental insights with computational advances, this work outlines a path for the rational design of next-generation SACs tailored to a broad spectrum of electrocatalytic applications. While summarizing the current landscape of electrocatalysis by SACs, it also outlines future directions to address the energy challenges of tomorrow, serving as a valuable resource for advancing the field.
Anthropogenic activities related to population growth, economic development, technological advances, and changes in lifestyle and climate patterns result in a continuous increase in energy consumption. At the same time, the rare metal elements frequently deployed as catalysts in energy related processes are not only costly in view of their low natural abundance, but their availability is often further limited due to geopolitical reasons. Thus, electrochemical energy storage and conversion with earth-abundant metals, mainly in the form of single-atom catalysts (SACs), are highly relevant and timely technologies. In this review the application of earth-abundant SACs in electrochemical energy storage and electrocatalytic conversion of chemicals to fuels or products with high energy content is discussed. The oxygen reduction reaction is also appraised, which is primarily harnessed in fuel cell technologies and metal-air batteries. The coordination, active sites, and mechanistic aspects of transition metal SACs are analyzed for two-electron and four-electron reaction pathways. Further, the electrochemical water splitting with SACs toward green hydrogen fuel is discussed in terms of not only hydrogen evolution reaction but also oxygen evolution reaction. Similarly, the production of ammonia as a clean fuel via electrocatalytic nitrogen reduction reaction is portrayed, highlighting the potential of earth-abundant single metal species.
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- Journal Article MeSH
- Review MeSH
Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society. The field of catalysis has been revolutionized by single-atom catalysts (SACs), which exhibit unique and intricate interactions between atomically dispersed metal atoms and their supports. Recently, bimetallic SACs (bimSACs) have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed supports. BimSACs offer an avenue for rich metal-metal and metal-support cooperativity, potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton-electron exchanges, substrate activation with reversible redox cycles, simultaneous multi-electron transfer, regulation of spin states, tuning of electronic properties, and cyclic transition states with low activation energies. This review aims to encapsulate the growing advancements in bimSACs, with an emphasis on their pivotal role in hydrogen generation via water splitting. We subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs, elucidate their electronic properties, and discuss their local coordination environment. Overall, we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction, the two half-reactions of the water electrolysis process.
- Keywords
- Hydrogen evolution, Oxygen evolution, Single-atom catalysts, Single-atom dimers, Water splitting,
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- Journal Article MeSH
- Review MeSH
A strategy for the synthesis of a gold-based single-atom catalyst (SAC) via a one-step room temperature reduction of Au(III) salt and stabilization of Au(I) ions on nitrile-functionalized graphene (cyanographene; G-CN) is described. The graphene-supported G(CN)-Au catalyst exhibits a unique linear structure of the Au(I) active sites promoting a multistep mode of action in dehydrogenative coupling of organosilanes with alcohols under mild reaction conditions as proven by advanced XPS, XAFS, XANES, and EPR techniques along with DFT calculations. The linear structure being perfectly accessible toward the reactant molecules and the cyanographene-induced charge transfer resulting in the exclusive Au(I) valence state contribute to the superior efficiency of the emerging two-dimensional SAC. The developed G(CN)-Au SAC, despite its low metal loading (ca. 0.6 wt %), appear to be the most efficient catalyst for Si-H bond activation with a turnover frequency of up to 139,494 h-1 and high selectivities, significantly overcoming all reported homogeneous gold catalysts. Moreover, it can be easily prepared in a multigram batch scale, is recyclable, and works well toward more than 40 organosilanes. This work opens the door for applications of SACs with a linear structure of the active site for advanced catalytic applications.
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- Journal Article MeSH
Heavy metal pollutants are of great concern to environmental monitoring due to their potent toxicity. Electrochemical detection, one of the main techniques, is hindered by the mutual interferences of various heavy metal ions in practical use. In particular, the sensitivity of carbon electrodes to Cd2+ ions (one of the most toxic heavy metals) is often overshadowed by some heavy metals (e.g. Pb2+ and Cu2+). To mitigate interference, metallic particles/films (e.g. Hg, Au, Bi, and Sn) typically need to be embedded in the carbon electrodes. However, these additional metallic materials may face issues of secondary pollution and unsustainability. In this study, a metal-free and sustainable nanomaterial, namely cysteamine covalently functionalized graphene (GSH), was found to lead to a 6-fold boost in the Cd2+ sensitivity of the screen-printed carbon electrode (SPCE), while the sensitivities to Pb2+ and Cu2+ were not influenced in simultaneous detection. The selective enhancement could be attributed to the grafted thiols on GSH sheets with good affinity to Cd2+ ions based on Pearson's hard and soft acid and base principle. More intriguingly, the GSH-modified SPCE (GSH-SPCE) featured high reusability with extended cycling times (23 times), surpassing the state-of-art SPCEs modified by non-covalently functionalized graphene derivatives. Last, the GSH-SPCE was validated in tap water.
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- Journal Article MeSH
Anchoring single metal atoms on suitable substrates is a convenient route towards materials with unique electronic and magnetic properties exploitable in a wide range of applications including sensors, data storage, and single atom catalysis (SAC). Among a large portfolio of available substrates, carbon-based materials derived from graphene and its derivatives have received growing concern due to their high affinity to metals combined with biocompatibility, low toxicity, and accessibility. Cyanographene (GCN) as highly functionalized graphene containing homogeneously distributed nitrile groups perpendicular to the surface offers exceptionally favourable arrangement for anchoring metal atoms enabling efficient charge exchange between the metal and the substrate. However, the binding characteristics of metal species can be significantly affected by the coordination effects. Here we employed density functional theory (DFT) calculations to analyse the role of coordination in the binding of late 3d cations (Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Cu+, and Zn2+) to GCN in aqueous solutions. The inspection of several plausible coordination types revealed the most favourable arrangements. Among the studied species, copper cations were found to be the most tightly bonded to GCN, which was also confirmed by the X-ray photoelectron spectroscopy (XPS), atomic absorption spectroscopy (AAS), and isothermal titration calorimetry (ITC) measurements. In general, the inclusion of coordination effects significantly reduced the binding affinities predicted by implicit solvation models. Clearly, to build-up reliable models of SAC architectures in the environments enabling the formation of a coordination sphere, such effects need to be properly taken into account.
Single-atom catalysts (SACs) based on graphene derivatives are an emerging and growing class of materials functioning as two-dimensional (2D) metal-coordination scaffolds with intriguing properties. Recently, owing to the rich chemistry of fluorographene, new avenues have opened toward graphene derivatives with selective, spacer-free, and dense functionalization, acting as in-plane or out-of-plane metal coordination ligands. The particular structural features give rise to intriguing phenomena occurring between the coordinated metals and the graphene backbone. These include redox processes, charge transfer, emergence, and stabilization of rare or otherwise unstable metal valence states, as well as metal-support and metal-metal synergism. The vast potential of such systems has been demonstrated as enzyme mimics for cooperative mixed-valence SACs, ethanol fuel cells, and CO2 fixation; however, it is anticipated that their impact will further expand toward diverse fields, e.g., advanced organic transformations, electrochemical energy storage, and energy harvesting.
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- Journal Article MeSH
- Review MeSH
Supercapacitors have attracted great interest because of their fast, reversible operation and sustainability. However, their energy densities remain lower than those of batteries. In the last decade, supercapacitors with an energy content of ∼110 W h L-1 at a power of ∼1 kW L-1 were developed by leveraging the open framework structure of graphene-related architectures. Here, we report that the reaction of fluorographene with azide anions enables the preparation of a material combining graphene-type sp2 layers with tetrahedral carbon-carbon bonds and nitrogen (pyridinic and pyrrolic) superdoping (16%). Theoretical investigations showed that the C-C bonds develop between carbon-centered radicals, which emerge in the vicinity of the nitrogen dopants. This material, with diamond-like bonds and an ultra-high mass density of 2.8 g cm-3, is an excellent host for the ions, delivering unprecedented energy densities of 200 W h L-1 at a power of 2.6 kW L-1 and 143 W h L-1 at 52 kW L-1. These findings open a route to materials whose properties may enable a transformative improvement in the performance of supercapacitor components.
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- Journal Article MeSH
In this work, the covalent attachment of an amine functionalized metal-organic framework (UiO-66-NH2 = Zr6 O4 (OH)4 (bdc-NH2 )6 ; bdc-NH2 = 2-amino-1,4-benzenedicarboxylate) (UiO-Universitetet i Oslo) to the basal-plane of carboxylate functionalized graphene (graphene acid = GA) via amide bonds is reported. The resultant GA@UiO-66-NH2 hybrid displayed a large specific surface area, hierarchical pores and an interconnected conductive network. The electrochemical characterizations demonstrated that the hybrid GA@UiO-66-NH2 acts as an effective charge storing material with a capacitance of up to 651 F g-1 , significantly higher than traditional graphene-based materials. The results suggest that the amide linkage plays a key role in the formation of a π-conjugated structure, which facilitates charge transfer and consequently offers good capacitance and cycling stability. Furthermore, to realize the practical feasibility, an asymmetric supercapacitor using a GA@UiO-66-NH2 positive electrode with Ti3 C2 TX MXene as the opposing electrode has been constructed. The cell is able to deliver a power density of up to 16 kW kg-1 and an energy density of up to 73 Wh kg-1 , which are comparable to several commercial devices such as Pb-acid and Ni/MH batteries. Under an intermediate level of loading, the device retained 88% of its initial capacitance after 10 000 cycles.
- Keywords
- 2D materials, MXenes, asymmetric supercapacitors, covalent assemblies, metal-organic frameworks,
- Publication type
- Journal Article MeSH
