Recent Advances in Electrocatalysts for Oxygen Reduction Reaction
TL;DR: This comprehensive Review focuses on the low- and non-platinum electrocatalysts including advanced platinum alloys, core-shell structures, palladium-based catalysts, metal oxides and chalcogenides, carbon-based non-noble metal catalysts and metal-free catalysts.
Abstract: The recent advances in electrocatalysis for oxygen reduction reaction (ORR) for proton exchange membrane fuel cells (PEMFCs) are thoroughly reviewed. This comprehensive Review focuses on the low- and non-platinum electrocatalysts including advanced platinum alloys, core–shell structures, palladium-based catalysts, metal oxides and chalcogenides, carbon-based non-noble metal catalysts, and metal-free catalysts. The recent development of ORR electrocatalysts with novel structures and compositions is highlighted. The understandings of the correlation between the activity and the shape, size, composition, and synthesis method are summarized. For the carbon-based materials, their performance and stability in fuel cells and comparisons with those of platinum are documented. The research directions as well as perspectives on the further development of more active and less expensive electrocatalysts are provided.
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TL;DR: This work shows that the performance of the commonly studied materials is limited by unfavorable scaling relationships (for binding energies of reaction intermediates), and presents a number of alternative strategies that may lead to the design and discovery of more promising materials for ORR.
Abstract: Despite the dedicated search for novel catalysts for fuel cell applications, the intrinsic oxygen reduction reaction (ORR) activity of materials has not improved significantly over the past decade. Here, we review the role of theory in understanding the ORR mechanism and highlight the descriptor-based approaches that have been used to identify catalysts with increased activity. Specifically, by showing that the performance of the commonly studied materials (e.g., metals, alloys, carbons, etc.) is limited by unfavorable scaling relationships (for binding energies of reaction intermediates), we present a number of alternative strategies that may lead to the design and discovery of more promising materials for ORR.
1,401 citations
TL;DR: In this review, the applications of MOFs with multiple active sites in synergistic organic catalysis, photocatalysis and tandem reactions are discussed and proposed mechanisms are presented in detail.
Abstract: Metal–organic frameworks (MOFs) are porous crystalline materials constructed from metal ions or clusters and multidentate organic ligands. Recently, the use of MOFs or MOF composites as catalysts for synergistic catalysis and tandem reactions has attracted increasing attention due to their tunable open metal centres, functional organic linkers, and active guest species in their pores. In this review, the applications of MOFs with multiple active sites in synergistic organic catalysis, photocatalysis and tandem reactions are discussed. These multifunctional MOFs can be categorized by the type of active centre as follows: (i) open metal centres and functional organic linkers in the MOF structure, (ii) active guest sites in the pores and active sites in the MOF structure, and (iii) bimetallic nanoparticles (NPs) on MOF supports. The types of synergistic catalysis and tandem reactions promoted by multifunctional MOFs and their proposed mechanisms are presented in detail. Here, catalytic MOFs with a single type of active site and MOFs that only serve as supports to enhance substrate adsorption are not discussed.
1,394 citations
TL;DR: Various cocatalysts, such as the biomimetic, metal-based,Metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area.
Abstract: Photoreduction of CO2 into sustainable and green solar fuels is generally believed to be an appealing solution to simultaneously overcome both environmental problems and energy crisis. The low selectivity of challenging multi-electron CO2 photoreduction reactions makes it one of the holy grails in heterogeneous photocatalysis. This Review highlights the important roles of cocatalysts in selective photocatalytic CO2 reduction into solar fuels using semiconductor catalysts. A special emphasis in this review is placed on the key role, design considerations and modification strategies of cocatalysts for CO2 photoreduction. Various cocatalysts, such as the biomimetic, metal-based, metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area. This Review provides useful information for the design of highly selective cocatalysts for photo(electro)reduction and electroreduction of CO2 and complements the existing reviews on various semiconductor photocatalysts.
1,365 citations
TL;DR: The fundamental relationships between electronic structure, adsorption energy, and apparent activity for a wide variety of 2D electrocatalysts are described with the goal of providing a better understanding of these emerging nanomaterials at the atomic level.
Abstract: Over the past few decades, the design and development of advanced electrocatalysts for efficient energy conversion technologies have been subjects of extensive study. With the discovery of graphene, two-dimensional (2D) nanomaterials have emerged as some of the most promising candidates for heterogeneous electrocatalysts due to their unique physical, chemical, and electronic properties. Here, we review 2D-nanomaterial-based electrocatalysts for selected electrocatalytic processes. We first discuss the unique advances in 2D electrocatalysts based on different compositions and functions followed by specific design principles. Following this overview, we discuss various 2D electrocatalysts for electrocatalytic processes involved in the water cycle, carbon cycle, and nitrogen cycle from their fundamental conception to their functional application. We place a significant emphasis on different engineering strategies for 2D nanomaterials and the influence these strategies have on intrinsic material performance, ...
1,363 citations
TL;DR: Common descriptors such as the substrate-hydroxide binding energy and the interactions in the double layer between hydroxide-oxides and H---OH are found to control individual parts of the hydrogen and oxygen electrochemistry that govern the efficiency of water-based energy conversion and storage systems.
Abstract: Advances in electrocatalysis at solid-liquid interfaces are vital for driving the technological innovations that are needed to deliver reliable, affordable and environmentally friendly energy. Here, we highlight the key achievements in the development of new materials for efficient hydrogen and oxygen production in electrolysers and, in reverse, their use in fuel cells. A key issue addressed here is the degree to which the fundamental understanding of the synergy between covalent and non-covalent interactions can form the basis for any predictive ability in tailor-making real-world catalysts. Common descriptors such as the substrate-hydroxide binding energy and the interactions in the double layer between hydroxide-oxides and H---OH are found to control individual parts of the hydrogen and oxygen electrochemistry that govern the efficiency of water-based energy conversion and storage systems. Links between aqueous- and organic-based environments are also established, encouraging the 'fuel cell' and 'battery' communities to move forward together.
1,345 citations
References
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TL;DR: Film and powders of TiO2-x Nx have revealed an improvement over titanium dioxide (TiO2) under visible light in optical absorption and photocatalytic activity such as photodegradations of methylene blue and gaseous acetaldehyde and hydrophilicity of the film surface.
Abstract: To use solar irradiation or interior lighting efficiently, we sought a photocatalyst with high reactivity under visible light. Films and powders of TiO 2- x N x have revealed an improvement over titanium dioxide (TiO 2 ) under visible light (wavelength 2 has proven to be indispensable for band-gap narrowing and photocatalytic activity, as assessed by first-principles calculations and x-ray photoemission spectroscopy.
11,402 citations
TL;DR: A comprehensive review of 1D nanostructures can be found in this article, where the authors provide a comprehensive overview of current research activities that concentrate on one-dimensional (1D) nanostructure (wires, rods, belts and tubes).
Abstract: This article provides a comprehensive review of current research activities that concentrate on one-dimensional (1D) nanostructures—wires, rods, belts, and tubes—whose lateral dimensions fall anywhere in the range of 1 to 100 nm. We devote the most attention to 1D nanostructures that have been synthesized in relatively copious quantities using chemical methods. We begin this article with an overview of synthetic strategies that have been exploited to achieve 1D growth. We then elaborate on these approaches in the following four sections: i) anisotropic growth dictated by the crystallographic structure of a solid material; ii) anisotropic growth confined and directed by various templates; iii) anisotropic growth kinetically controlled by supersaturation or through the use of an appropriate capping reagent; and iv) new concepts not yet fully demonstrated, but with long-term potential in generating 1D nanostructures. Following is a discussion of techniques for generating various types of important heterostructured nanowires. By the end of this article, we highlight a range of unique properties (e.g., thermal, mechanical, electronic, optoelectronic, optical, nonlinear optical, and field emission) associated with different types of 1D nanostructures. We also briefly discuss a number of methods potentially useful for assembling 1D nanostructures into functional devices based on crossbar junctions, and complex architectures such as 2D and 3D periodic lattices. We conclude this review with personal perspectives on the directions towards which future research on this new class of nanostructured materials might be directed.
8,259 citations
TL;DR: In this paper, the stability of reaction intermediates of electrochemical processes on the basis of electronic structure calculations was analyzed and a detailed description of the free energy landscape of the electrochemical oxygen reduction reaction over Pt(111) as a function of applied bias was presented.
Abstract: We present a method for calculating the stability of reaction intermediates of electrochemical processes on the basis of electronic structure calculations. We used that method in combination with detailed density functional calculations to develop a detailed description of the free-energy landscape of the electrochemical oxygen reduction reaction over Pt(111) as a function of applied bias. This allowed us to identify the origin of the overpotential found for this reaction. Adsorbed oxygen and hydroxyl are found to be very stable intermediates at potentials close to equilibrium, and the calculated rate constant for the activated proton/electron transfer to adsorbed oxygen or hydroxyl can account quantitatively for the observed kinetics. On the basis of a database of calculated oxygen and hydroxyl adsorption energies, the trends in the oxygen reduction rate for a large number of different transition and noble metals can be accounted for. Alternative reaction mechanisms involving proton/electron transfer to ...
7,711 citations
IBM1
TL;DR: Thermal annealing converts the internal particle structure from a chemically disordered face- centered cubic phase to the chemically ordered face-centered tetragonal phase and transforms the nanoparticle superlattices into ferromagnetic nanocrystal assemblies that can support high-density magnetization reversal transitions.
Abstract: Synthesis of monodisperse iron-platinum (FePt) nanoparticles by reduction of platinum acetylacetonate and decomposition of iron pentacarbonyl in the presence of oleic acid and oleyl amine stabilizers is reported. The FePt particle composition is readily controlled, and the size is tunable from 3- to 10-nanometer diameter with a standard deviation of less than 5%. These nanoparticles self-assemble into three-dimensional superlattices. Thermal annealing converts the internal particle structure from a chemically disordered face-centered cubic phase to the chemically ordered face-centered tetragonal phase and transforms the nanoparticle superlattices into ferromagnetic nanocrystal assemblies. These assemblies are chemically and mechanically robust and can support high-density magnetization reversal transitions.
5,568 citations
TL;DR: Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity, high thermal stability, and remarkable chemical resistance to boiling alkaline water and organic solvents.
Abstract: Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) have been synthesized as crystals by copolymerization of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, respectively. In addition, one example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m 2 /g), high thermal stability (up to 550°C), and remarkable chemical resistance to boiling alkaline water and organic solvents.
5,512 citations