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Platinum metal (PtM, M=Ni, Fe, Co) alloys catalysts show high oxygen reduction reaction (ORR) activity due to their well‐known strain and ligand effects. However, these PtM alloys usually suffer from a deficient ORR durability in acidic environment as the alloyed metal is prone to be dissolved due to its high electronegativity. Herein, we report a new class of PtMn alloy nanodendrite catalyst with low‐electronegativity Mn‐contraction for boosting the oxygen reduction durability of fuel cells. The moderate strain in PtMn, induced by Mn contraction, yields optimal oxygen reduction activity at 0.53 A mg−1 at 0.9 V versus reversible hydrogen electrode (RHE). Most importantly, we show that relative to well‐known high‐electronegativity Ni‐based Pt alloy counterpart, the PtMn nanodendrite catalyst experiences less transition metals' dissolution in acidic solution and achieves an outstanding mass activity retention of 96 % after 10,000 degradation cycles. Density functional theory calculation reveals that PtMn alloys are thermodynamically more stable than PtNi alloys in terms of formation enthalpy and cohesive energy. The PtMn nanodendrite‐based membrane electrode assembly delivers an outstanding peak power density of 1.36 W cm−2 at a low Pt loading and high‐performance retention over 50 h operations at 0.6 V in H2‐O2 hydrogen fuel cells. [ABSTRACT FROM AUTHOR]

Spreading the formic acid (HCOOH) fuel cells demands a better anode electrocatalyst for the oxidation of formic acid. The catalytic efficiency of platinum (Pt)– the only choice of practicability, is mainly limited by its intrinsic affinity to CO, thus desiring a proper release. Herein, theoretical calculations are first leveraged to find that the introduction of iridium (Ir) can facilitate HCOOH oxidation with robust CO tolerance through a dehydrogenation pathway. Then, this strategy experimentally by designing a new trimetallic catalyst of 2D porous PtIrBi nanoplates (p‐PtIrBi NPs) is implemented. The optimized p‐PtIrBi NPs/C exhibits a very high mass activity of 8.2 A mg−1pt and a high retention rate of 55.9% after the durability test, which is among the best formic acid oxidation catalysts reported to date, much higher than those of PtIrBi NPs/C, PtBi NPs/C, and Pt/C. The CO‐stripping and in situ Fourier transform infrared (FTIR) experiments collectively evidence that two types of due site, i.e., "Pt‐Bi" and "Ir‐Bi", endow the catalyst with suppressed CO‐poisoning property to achieve super‐high activity and stability for formic acid oxidation reaction. [ABSTRACT FROM AUTHOR]

Palladium (Pd)‐based materials have attracted increasing attentions as a kind of novel candidate catalysts for many electrocatalytic reactions to replace classic platinum (Pt) catalysts, especially in the fuel cell‐related electrocatalysis. However, the requirement of high activity and stability toward further practical applications makes the development of Pd‐based catalysts cease to advance. Combining alloying and structure‐controlled strategies has well addressed this challenge by optimizing the adsorption/desorption behaviors toward reaction intermediates. Herein, the recent advances of rational structural designs in terms of tuning the dimensionalities of Pd‐based nanoalloys are overviewed. To further enhance the intrinsic electrocatalytic activity, several advanced strategies, including intermetallics, doping, defects, surface, and interface engineering, are presented to engineer the electronic and/or physical properties of Pd‐based electrocatalysts. Using typical electrocatalytic reactions as probes, the significance of structural regulation of Pd‐based nanocrystals on the enhanced electrocatalysis is demonstrated. Finally, several possible trends and challenges for future advanced research directions are presented. It is anticipated that the rational structural regulation can make promising Pd‐based catalysts touch the ceiling of electrocatalytic activity and stability. [ABSTRACT FROM AUTHOR]

Ultrathin nanosheet catalysts deliver great potential in catalyzing the oxygen reduction reaction (ORR), but encounter the ceiling of the surface atomic utilizations, thus presenting a challenge associated with further boosting catalytic activity. Herein, a kind of PdPtCu ultrathin nanorings with increased numbers of electrocatalytically active sites is reported, with the purpose of breaking the activity ceiling of conventional catalysts. The as‐made PdPtCu nanorings possess abundant high‐index facets at the edge of both the exterior and interior surfaces. An ultrahigh electrochemical active surface area of 92.2 m2 g–1PGM is achieved on this novel catalyst, much higher than that of the commercial Pt/C catalyst. The optimized Pd39Pt33Cu28/C shows a great enhanced ORR activity with a specific activity of 2.39 mA cm–2 and a mass activity of 1.97 A mg–1PGM at 0.9 V (versus RHE), as well as superior durability within 30 000 cycles. Density function theory calculations reveal that the high‐index facets and alloying Cu atoms can optimize the oxygen adsorption energy, explaining the enhanced ORR activity. Overcoming a key technical barrier in sub‐nanometer electrocatalysts, this work successfully introduces the hollow structures into the ultrathin nanosheets, heralding the exciting prospects of high‐performance ORR catalysts in fuel cells. [ABSTRACT FROM AUTHOR]

Abstract: The development of high‐performance oxygen reduction reaction (ORR) catalysts derived from non‐Pt group metals (non‐PGMs) is urgent for the wide applications of proton exchange membrane fuel cells (PEMFCs). In this work, a facile and cost‐efficient supramolecular route is developed for making non‐PGM ORR catalyst with atomically dispersed Fe‐Nx/C sites through pyrolyzing the metal‐organic polymer coordinative hydrogel formed between Fe3+ and α‐L‐guluronate blocks of sodium alginate (SA). High‐angle annular dark field scanning transmission electron microscopy (HAADF‐STEM) and X‐ray absorption spectroscopy (XAS) verify that Fe atoms achieve atomic‐level dispersion on the obtained SA‐Fe‐N nanosheets and a possible fourfold coordination with N atoms. The best‐performing SA‐Fe‐N catalyst exhibits excellent ORR activity with half‐wave potential (E1/2) of 0.812 and 0.910 V versus the reversible hydrogen electrode (RHE) in 0.5 m H2SO4 and 0.1 m KOH, respectively, along with respectable durability. Such performance surpasses that of most reported non‐PGM ORR catalysts. Density functional theory calculations suggest that the relieved passivation effect of OH* on Fe‐N4/C structure leads to its superior ORR activity to Pt/C in alkaline solution. The work demonstrates a novel strategy for developing high‐performance non‐PGM ORR electrocatalysts with atomically dispersed and stable M‐Nx coordination sites in both acidic and alkaline media. [ABSTRACT FROM AUTHOR]

Depositing Pt atoms on nanoscale two-dimensional (2D) substrates resulting in the exposure of specific crystal facets is an effective strategy for reducing the Pt content without compromising the catalytic property. Herein, the Pd/PtCu core/shell nanoplates exhibit substantially improved ORR and MOR mass activities, 8.3 and 3.3 times higher than those of commercial Pt. The present work highlights the important role of designing a 2D core/shell nanostructure in enhancing fuel cell electrocatalysis. [ABSTRACT FROM AUTHOR]

Ordered intermetallic alloys have attracted extensive attention as advanced electrocatalysts for polymer electrolyte membrane fuel cells (PEMFCs) reactions with much improved activity and stability. Here, latest progress in tuning intermetallic Pt- and Pd-based nanocrystals with tunable morphology and structure for catalyzing both the cathodic reduction of oxygen and anodic oxidation of fuels (e.g., methanol, ethanol and formic acid) in PEMFCs is highlighted. Making/tuning interesting intermetallic PtM (M = Fe, Co, Pb, Cu, etc.)-based nanocrystals for boosting oxygen reduction reaction with high activity and stability by using/controlling high-temperature annealing treatment is discussed. In all the reported Pt-based intermetallic nanocrystals, controlling the degree of ordering under the proper high temperature treatment is the key for achieving the optimized electrocatalysis. In order to search for cheaper catalysts, the progress on making Pd-based intermetallic nanocrystals is also discussed. Furthermore, future research directions are proposed and discussed to further enhance the efficiency of such unique intermetallic multimetallic nanocatalysts. This report aims to demonstrate the potential of ordered intermetallic strategy for boosting electrocatalysis and stimulating more research efforts in this field. [ABSTRACT FROM AUTHOR]

The development of superior non-platinum electrocatalysts for enhancing the electrocatalytic activity and stability for the oxygen-reduction reaction (ORR) and liquid fuel oxidation reaction is very important for the commercialization of fuel cells, but still a great challenge. Herein, we demonstrate a new colloidal chemistry technique for making structurally ordered PdCu-based nanoparticles (NPs) with composition control from PdCu to PdCuNi and PtCuCo. Under the dual tuning on the composition and intermetallic phase, the ordered PdCuCo NPs exhibit better activity and much enhanced stability for ORR and ethanol-oxidation reaction (EOR) than those of disordered PdCuM NPs, the commercial Pt/C and Pd/C catalysts. The density functional theory (DFT) calculations reveal that the improved ORR activity on the PdCuM NPs stems from the catalytically active hollow sites arising from the ligand effect and the compressive strain on the Pd surface owing to the smaller atomic size of Cu, Co, and Ni. [ABSTRACT FROM AUTHOR]

Replacing the rare and precious platinum (Pt) electrocatalysts with earth-abundant materials for promoting the oxygen reduction reaction (ORR) at the cathode of fuel cells is of great interest in developing high-performance sustainable energy devices. However, the challenging issues associated with non-Pt materials are still their low intrinsic catalytic activity, limited active sites, and the poor mass transport properties. Recent advances in material sciences and nanotechnology enable rational design of new earth-abundant materials with optimized composition and fine nanostructure, providing new opportunities for enhancing ORR performance at the molecular level. This Review highlights recent breakthroughs in engineering nanocatalysts based on the earth-abundant materials for boosting ORR. [ABSTRACT FROM AUTHOR]

Herein, a novel tunable electrocatalytic nanobiointerface for the construction of a high-sensitivity and high-selectivity biofuel-cell (BFC)-based self-powered biosensor for the detection of transcription factor protein p53 is reported, in which bilirubin oxidase (BOD)/DNA supramolecular modified graphene/platinum nanoparticles hybrid nanosheet (GPNHN) works as a new enhanced material of biocathode to control the attachment of target, and thus tune the electron-transfer process of oxygen reduction for transducing signaling magnification. It is found that in the presence of p53, the strong interaction between the wild-type p53 and its consensus DNA sequence on the electrode surface can block the electron transfer from the BOD to the electrode, thus providing a good opportunity for reducing the electrocatalytic activity of oxygen reduction in the biocathode. This in combination with the glucose oxidation at the carbon nanotube/Meldola's blue/glucose dehydrogenase bioanode can result in a current/or power decrease of BFC in the presence of wild-type p53. The specially designed BFC-based self-powered p53 sensor shows a wide linear range from 1 p M to 1 μ M with a detection limit of 1 p M for analyzing wild-type p53. Most importantly, our BFC-based self-powered sensors can detect the concentrations of wild-type p53 in normal and cancer cell lysates without any extensive sample pretreatment/separation or specialized instruments. The present BFC-based self-powered sensor can provide a simple, economical, sensitive, and rapid way for analyzing p53 protein in normal and cancer cells at clinical level, which shows great potential for creating the treatment modalities that capitalize on the concentration variation of the wild-type p53. [ABSTRACT FROM AUTHOR]

A TiO2 nanotube photoanode is introduced into H2O2‐based fuel cells to improve their performance by utilizing light energy and biomass power. Upon UV illumination, the light‐driven, membraneless, H2O2‐based fuel cells exhibit a high open‐circuit potential (OCP) of 0.595 V and stable power density of 90 μW cm–2. [ABSTRACT FROM AUTHOR]

Pt-based nanostructures serving as anode catalysts for the methanol oxidation reaction (MOR) have been widely studied for many years. Nevertheless, challenging issues such as poor reaction kinetics and the short-term stability of the MOR are the main drawbacks of such catalysts and limit their applications. Herein, we have developed a facile approach to encapsulate Pt nanoparticles (NPs) inside the nanochannels of porous carbon nanotubes (CNTs; Pt-in-CNTs) as a new enhanced electrocatalytic material. The as-prepared CNTs offer simultaneously ordered diffusion channels for ions and a confinement effect for the NPs, which both facilitate the promotion of catalytic kinetics and avoid the Ostwald ripening of Pt NPs, thus leading to high activity and durable cycle life as an anode catalyst for MOR. This work provides a new approach for enhancing the stability and activity by optimizing the structure of the catalyst, and the Pt-in-CNTs represent the most durable catalysts ever reported for MOR. [ABSTRACT FROM AUTHOR]

Advances in chemical syntheses have led to the formation of various kinds of nanoparticles (NPs) with more rational control of size, shape, composition, structure and catalysis. This review highlights recent efforts in the development of Pt and non-Pt based NPs into advanced nanocatalysts for efficient oxygen reduction reaction (ORR) under fuel-cell reaction conditions. It first outlines the shape controlled synthesis of Pt NPs and their shape-dependent ORR. Then it summarizes the studies of alloy and core-shell NPs with controlled electronic (alloying) and strain (geometric) effects for tuning ORR catalysis. It further provides a brief overview of ORR catalytic enhancement with Pt-based NPs supported on graphene and coated with an ionic liquid. The review finally introduces some non-Pt NPs as a new generation of catalysts for ORR. The reported new syntheses with NP parameter-tuning capability should pave the way for future development of highly efficient catalysts for applications in fuel cells, metal-air batteries, and even in other important chemical reactions. [ABSTRACT FROM AUTHOR]

We have demonstrated a rapid and general strategy to synthesize novel three-dimensional PdPt bimetallic alloy nanosponges in the absence of a capping agent. Significantly, the as-prepared PdPt bimetallic alloy nanosponges exhibited greatly enhanced activity and stability towards ethanol/methanol electrooxidation in an alkaline medium, which demonstrates the potential of applying these PdPt bimetallic alloy nanosponges as effective electrocatalysts for direct alcohol fuel cells. In addition, this simple method has also been applied for the synthesis of AuPt, AuPd bimetallic, and AuPtPd trimetallic alloy nanosponges. The as-synthesized three-dimensional bimetallic/trimetallic alloy nanosponges, because of their convenient preparation, well-defined sponge-like network, large-scale production, and high electrocatalytic performance for ethanol/methanol electrooxidation, may find promising potential applications in various fields, such as formic acid oxidation or oxygen reduction reactions, electrochemical sensors, and hydrogen-gas sensors. [ABSTRACT FROM AUTHOR]

In order to develop new, high technology devices for a variety of applications, researchers would like to better control the structure and function of micro/nanomaterials through an understanding of the role of size, shape, architecture, composition, hybridization, molecular engineering, assembly, and microstructure. However, researchers continue to face great challenges in the construction of well-defined micro/nanomaterials with diverse morphologies. At the same time, the research interface where micro/nanomaterials meet electrochemistry, analytical chemistry, biomedicine, and other fields provides rich opportunities to reveal new chemical, physical, and biological properties of micro/nanomaterials and to uncover many new functions and applications of these materials. In this Account, we describe our recent progress in the construction of novel inorganic and polymer nanostructures formed through different simple strategies. Our synthetic strategies include wet-chemical and electrochemical methods for the controlled production of inorganic and polymer nanomaterials with well-defined morphologies. These methods are both facile and reliable, allowing us to produce high-quality micro/nanostructures, such as nanoplates, micro/nanoflowers, monodisperse micro/nanoparticles, nanowires, nanobelts, and polyhedron and even diverse hybrid structures. We implemented a series of approaches to address the challenges in the preparation of new functional micro/nanomaterials for a variety of important applications This Account also highlights new or enhanced applications of certain micro/nanomaterials in sensing applications. We singled out analytical techniques that take advantage of particular properties of micro/nanomaterials. Then by rationally tailoring experimental parameters, we readily and selectively obtained different types of micro/nanomaterials with novel morphologies with high performance in applications such as electrochemical sensors, electrochemiluminescent sensors, gene delivery agents, and fuel cell catalysts. We expect that micro/nanomaterials with unique structural characteristics, properties, and functions will attract increasing research interest and will lead to new opportunities in various fields of research. [ABSTRACT FROM AUTHOR]

Summary: Nobel metal nanomaterials (NMNs) with interesting physical and chemical properties are ideal building blocks for engineering and tailoring nanoscale structures for specific technological applications. Particularly, effectively controlling the size, shape, architecture, composition, hybrid and microstructure of NMNs plays an important role on revealing their new or enhanced functions and application potentials such as fuel cell and analytical sensors. This review article focuses on recent advances on controllable synthesis and fuel cell and sensing applications of NMNs. First, recent contributions on developing a wet-chemical approach for the controllable synthesis of noble metal nanomaterials with a rich variety of shapes, e.g. single-component Pt, Pd, Ag and Au nanomaterials, multi-component core/shell, intermetallic or alloyed nanomaterials, metal fluorescent nanoclusters and metal nanoparticles-based hybrid nanomaterials, are summarized. Then diversified approaches to different types of NMNs-based nanoelectrocatalysts with the aim to enhance their activity and durability for fuel cell reactions are outlined. The review next introduces some exciting push in the use of NMNs as enhanced materials or reporters or labels for developing new analytical sensors including electrochemical, colorimetric and fluorescent sensors. Finally, we conclude with a look at the future challenges and prospects of the development of NMNs. [ABSTRACT FROM AUTHOR]

An introduction is presented in which the editor discusses articles in the issue on topics including solar cells, electrocatalysis, batteries, and supercapacitors.

Graphical abstract Abstract Direct methanol fuel cells (DMFCs) have received extensive attention on their high efficiency, high reliability, and no carbon emission. Unfortunately, the poor methanol tolerance and sluggish oxygen reduction reaction (ORR) at cathode have seriously hindered their further development. Herein we report the synthesis of a new class of Rh-doped PdAg alloy nanoparticles (NPs) for boosting ORR activity with high methanol tolerance capacity concurrently. The ORR mass activity of typical Rh 4 Pd 40 Ag 56 NPs is 4.2 times higher than that of commercial Pt catalyst. Moreover, it shows a great methanol tolerance capability by maintaining 92.4% in ORR mass activity in alkaline solution with 0.1 mol L−1 methanol, against a big decrease of almost 100% for commercial Pt. Even after 30,000 potential cycles with 1.0 mol L−1 methanol, Rh 4 Pd 40 Ag 56 NPs still retain ORR mass activity of up to 68.3%. DFT calculations reveal that excellent ORR performance with excellent methanol tolerance originates the active d-band-pinning engineering for an efficient site-independent electron-transfer. A generalized d-band mediated fine electron-transfer tuning path has blueprinted for effectively minimizing intrinsic ORR barriers with high current density. The present work highlights the key role of Rh doping in enhancing the ORR activity and methanol tolerance ability of PdAg NPs for future high-performance DMFCs. [ABSTRACT FROM AUTHOR]