Exploring nonprecious metal electrocatalysts to replace the noble metal-based catalysts for full water electrocatalysis is still an ongoing challenge. In this work, porous structured ternary nickel–iron–phosphide (Ni–Fe–P) nanocubes were synthesized through one-step phosphidation of a Ni–Fe-based Prussian blue analogue. The Ni–Fe–P nanocubes exhibit a rough and loose porous structure on their surface under suitable phosphating temperature, which is favorable for the mass transfer and oxygen diffusion during the electrocatalysis process. As a result, Ni–Fe–P obtained at 350 °C with poorer crystallinity offers more unsaturated atoms as active sites to expedite the absorption of reactants. Additionally, the introduction of nickel improved the electronic structure and then reduced the charge-transfer resistance, which would result in a faster electron transport and an enhancement of the intrinsic electrocatalytic activities. Benefiting from the unique porous nanocubes and the chemical composition, the Ni–Fe–P...

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Porous Structured Ni–Fe–P Nanocubes Derived from a Prussian Blue Analogue as an Electrocatalyst for Efficient Overall Water Splitting

Highly efficient earth-abundant electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are of great importance for renewable energy conversion systems. Herein, hollow porous heterometallic phosphide nanocubes are developed as a highly active and robust catalyst for electrochemical water splitting via one-step phosphidation of a NiCoFe Prussian blue analogue. Through modulation of the composition of metals in the precursors, the optimal NiCoFeP exhibiting increased electrical conductivity and abundant electrochemically active sites, leading to high electrocatalytic activities and outstanding kinetics for both HER and OER, is successfully obtained. NiCoFeP shows low overpotentials of 273 mV for OER and 131 mV for HER at a current density of 10 mA cm-2 and quite low Tafel slopes of 35 mV dec-1 for OER and 56 mV dec-1 for HER.

Hollow Porous Heterometallic Phosphide Nanocubes for Enhanced Electrochemical Water Splitting.

Metal-organic frameworks (MOFs), formed by the self-assembly of metal centres or clusters and organic linkers, possess many key structural and chemical features that have enabled them to be used in sensing platforms for a variety of environmentally, chemically and biomedically relevant compounds. In particular, their high porosity, large surface area, tuneable chemical composition, high degree of crystallinity, and potential for post-synthetic modification for molecular recognition make MOFs promising candidates for biosensing applications. In this review, we separate our discussion of MOF biosensors into two categories: quantitative sensing, focusing specifically on luminescence-based sensors for the direct measurement of a specific analyte, and qualitative sensing, where we describe MOFs used for fluorescence microscopy and as magnetic resonance imaging contrast agents. We highlight several key publications in each of these areas, concluding that MOFs present an exciting, versatile new platform for biosensing applications and imaging, and we expect to see their usage grow as the field progresses.

https://royalsocietypublishing.org/doi/pdf/10.1098/rsfs.2016.0027

Metal-organic frameworks as biosensors for luminescence-based detection and imaging.

Enhanced adsorption of cesium on PVA-alginate encapsulated Prussian blue-graphene oxide hydrogel beads in a fixed-bed column system

Exploring highly efficient and cost-effective electrocatalysts for the oxygen evolution reaction (OER) is becoming increasingly important in the field of sustainable energy systems. In this work, a three dimensional (3D) hierarchical porous nickel and iron based sulfide (Ni–Fe–S) with a sea urchin-like morphology is synthesized by a facile sulfurization of Prussian blue analogue (PBA) precursors with a hydrothermal reaction and post-calcination treatment. The mass ratio of PBA and sulfur sources, the hydrothermal temperature and time, and the presence of hydrazine hydrate are found to be important factors for the formation of the unique sea urchin-like materials with the porous carbon layer and mixed phases of Fe5Ni4S8 and NiS, which are conducive to fast mass and charge transfer along various directions, endow the materials with mixed valences, improve the electronic conductivity and prevent the agglomeration of nanostructured sulfides. Benefiting from these fascinating advantages, the optimal Ni–Fe–S catalyst exhibits excellent catalytic activities with an overpotential as low as 200 mV to attain a current density of 10 mA cm−2 and good stability toward the OER. This work not only offers a facile strategy to prepare efficient transition metal based sulfides with excellent electrocatalytic activity for the OER but also extends the synthesis and application of PBA-derived nanostructured materials.

Sea urchin-like Ni–Fe sulfide architectures as efficient electrocatalysts for the oxygen evolution reaction

The CoFe Prussian blue analogue/carbon nanotube composite material was synthesized and applied to catalyze the reaction of epoxidation of styrene. Carbon nanotubes were used as catalyst carriers. The catalytic activity of this composite material was superior to the CoFe Prussian blue analogue and carbon nanotubes taken independently. The composite material indeed had a larger surface area and a better particle dispersion than the bulk Prussian blue analogue. Kinetic studies were also carried out. The reaction activation energy of the CoFe Prussian blue analogue alone was equal to 75.83 kJ mol−1, while the reaction activation energy of the composite material was equal to 35.67 kJ mol−1. A first order reaction with respect to the concentrations of catalyst, styrene and tert-butyl hydroperoxide was also determined. The composite catalyst could be reused for up to five cycles without any significant loss in conversion and selectivity.

Synthesis of CoFe Prussian blue analogue/carbon nanotube composite material and its application in the catalytic epoxidation of styrene

The modification of carbon cloth (CC) with Prussian blue (PB) and chitosan (CS) leads to the elaboration of a composite electrode (PB/CS/CC), employed to electrocatalyze the oxidation of ascorbic acid (AA). This electrode exhibits great performances towards the AA detection, thanks to the good conductivity of CC and the efficient catalytic properties of PB. The modified electrode shows a rapid response of less than 2 s, a very high sensitivity of 1.64 A ⋅ M−1 and a good resistance towards common interferences. Its linear range goes from 3×10−7 M to 3×10−4 M (R2=0.993), with a detection limit (S/N=3) of 2.50×10−7 M. Finally, such electrode can detect AA in commercial vitamin C; it is thus a good candidate as a simple and convenient sensor for general applications.

Prussian Blue and Chitosan Modified Carbon Cloth Electrode as a High Performance Sensor of Ascorbic Acid

In this article, a new application of the room temperature ionic liquid, tetramethylammonium tetrafluoroborate, is described. This ionic liquid is used as a stabilizing agent and the reaction medium for the synthesis of CoFe Prussian blue analogue nanoparticles using N,N-dimethyl formamide as a complexing agent. The as-synthesized Prussian blue analogues were characterized by various techniques and were used to catalyze the reaction of epoxidation of styrene. The catalytic activity of Prussian blue analogues prepared in ionic liquid was superior to that of Prussian blue analogues prepared in aqueous solution.

Simple synthesis of Prussian blue analogues in room temperature ionic liquid solution and their catalytic application in epoxidation of styrene

Effect of cesium ion on the synthesis and catalytic properties with FeCo Prussian blue analogue

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Synthesis of CoFe Prussian blue analogue/carbon nanotube composite material and its application in the catalytic epoxidation of styrene

Prussian Blue and Chitosan Modified Carbon Cloth Electrode as a High Performance Sensor of Ascorbic Acid

Simple synthesis of Prussian blue analogues in room temperature ionic liquid solution and their catalytic application in epoxidation of styrene

Effect of cesium ion on the synthesis and catalytic properties with FeCo Prussian blue analogue