PdPt alloy nanocubes as electrocatalysts for oxygen reduction reaction in acid media

In this work, PdPt alloy nanocubes with different metal ratios were synthesised in the presence of polyvinylpyrrolidone (PVP). The surface morphology of the PdPt samples was characterised by transmission electron microscopy (TEM). TEM images showed that PdPt nanoparticles were cubic-shaped and the average size of the cubes was about 8–10 nm. Their electrocatalytic activity towards the oxygen reduction reaction (ORR) was studied in 0.5 M H2SO4 using the rotating disc electrode method. All the alloyed catalysts showed enhanced electrocatalytic activity for ORR as compared to the monometallic cubic Pd nanoparticles. Half-wave potential values for PdPt catalysts were comparable with that of Pt nanocubes. From the alloyed catalysts Pd36Pt64 exhibited the highest specific activity, which was only slightly lower than that of cubic Pt nanoparticles. The Koutecky–Levich analysis revealed that the reduction of oxygen proceeded via 4-electron pathway on all the electrocatalysts studied.This research was financially supported by institutional research funding (IUT20-16) of the Estonian Ministry of Education and Research and by the Estonian Research Council (Grant No. 9323) and by Archimedes Foundation (Project No. 3.2.0501.10-0015). KJ thanks the Archimedes Foundation for scholarship. JMF acknowledges financial support from MINECO (Spain), project CTQ2013-44083-P

Loading effect of carbon-supported platinum nanocubes on oxygen electroreduction

In this work, Vulcan carbon-supported cube-shape Pt nanoparticles with various metal loadings were synthesised in the presence of oleylamine and oleic acid. Surface morphology of different Pt/C samples was examined by transmission electron microscopy (TEM) and their metal loading verified by thermogravimetric analysis (TGA). TEM micrographs showed Pt nanoparticles with a preferential cubic-shape and increased agglomeration of the particles with increasing Pt loading. Electrochemical characterisation of the Pt/C catalysts indicated that the resulting Pt nanoparticles present a preferential (100) surface structure. The electrocatalytic properties of the Pt/C catalysts of different metal loading were evaluated towards the oxygen reduction reaction (ORR) both in acidic and alkaline media employing the rotating disk electrode (RDE) configuration. Interestingly, similar specific and mass activities were found in both solutions revealing that the ORR activities were independent of the Pt loading and suggesting that all the Pt nanocubes contributed as isolated particles.This work was financially supported by institutional research funding (IUT20-16) of the Estonian Ministry of Education and Research. This research was also supported by the EU through the European Regional Development Fund (TK141 “Advanced materials and high-technology devices for energy recuperation systems”). KJ would like to thank Archimedes Foundation for the partial study scholarship. JMF thanks MINECO (Project CTQ2016-76221-P (AEI/FEDER, UE)) and Generalitat Valenciana (Project PROMETEOII/2014/013) for financial support. JSG acknowledges financial support from VITC (Vicerrectorado de Investigación y Transferencia de Conocimiento) of the University of Alicante

Geometry-adaptive catalysts for elevating towards the ideal oxygen electrocatalysis

This communication introduces the concept of geometry-adaptive electrocatalysis, where catalysts adjust their geometry during the reaction. A model system of metal-nitrogen-carbon (M-N-C) catalysts – the dual-atom site 2Co-N₄ of variable curvature – proves the concept at the Density Functional Theory level. Calculations show how combining the geometric curvature effect with a geometry-adaptive cycle bypasses the known fundamental limitation due to scaling relations. Thus, in theory, geometry-adaptive electrocatalysis offers a promising direction to address the current stagnation in the experimentally measured overpotential for oxygen evolution and reduction reactions. It also indicates the possibility of discovering the ideal oxygen electrocatalyst catalyst

Multifunctional Electrocatalysis on Single-Site Metal Catalysts: A Computational Perspective

Multifunctional electrocatalysts are vastly sought for their applications in water splitting electrolyzers, metal-air batteries, and regenerative fuel cells because of their ability to catalyze multiple reactions such as hydrogen evolution, oxygen evolution, and oxygen reduction reactions. More specifically, the application of single-atom electrocatalyst in multifunctional catalysis is a promising approach to ensure good atomic efficiency, tunability and additionally benefits simple theoretical treatment. In this review, we provide insights into the variety of single-site metal catalysts and their identification. We also summarize the recent advancements in computational modeling of multifunctional electrocatalysis on single-site catalysts. Furthermore, we explain each modeling step with open-source-based working examples of a standard computational approach

Liquid-assisted grinding/compression: a facile mechanosynthetic route for the production of high-performing Co–N–C electrocatalyst materials

This research was supported by the Estonian Research Council grant PSG250; and by the EU through the European Regional Development Fund (TK141, “Advanced materials and high-technology devices for energy recuperation systems” and TK143, “Molecular Cell Engineering”).Worldwide implementation of energy conversion devices such as metal–air batteries and fuel cells needs an innovative approach for the sustainable design of noble metal-free electrocatalysts. A key factor to be considered is the industry-scale production method, which should be cost and energy-effective, and environmentally friendly. A novel solid-phase-based methodology is introduced herein as a new approach for the mechanosynthesis of M–N–C-type catalysts. This method employs low-cost commercially available materials, is time and energy-efficient, results in no solvent/toxic waste and does not require a complex post-synthetic treatment. The liquid-assisted grinding/compression approach yielded a series of meso- and microporous Co–N–C catalysts, with excellent bifunctional activity towards oxygen evolution and reduction reactions. In-depth physical characterization confirmed that all NaCl-supported catalysts possess cross-linked sheet-like mesoporous carbon structures with high exposure of catalytically active sites. This study provides a new avenue for the large-scale production of high-performance and low-cost M–N–C materials via energy-effective and environmentally sustainable synthetic protocols. This journal is © The Royal Society of Chemistry.Estonian Research Council grant PSG250; ERDF TK141 and TK143; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART2

Oxygen reduction reaction on nanostructured Pt-based electrocatalysts: A review

Pt deposition/anchoring technique and nature of the support influence the oxygen reduction reaction (ORR) activity in low-temperature proton exchange membrane fuel cells. Surface distribution, morphology (particle shape and size) of the deposited Pt nanoparticles (NPs) and physicochemical properties contribute to the electrocatalytic activity and durability of the catalyst. Investigations over the past two decades lead to various metal and metal oxide-based supports, along with advanced nanocarbon materials as suitable candidates since they play a vital role in defining surface morphology, particle-size distribution, crystallinity and electronic structure of the deposited Pt catalyst. Moreover, such supports improve the ORR activity and stability of the electrocatalyst due to their stronger interaction with the deposited Pt NPs. Briefly, a well-controlled and selective deposition of Pt NPs and designing of an excellent corrosion-resistant support for a promising ORR catalyst has gained more attention. Many advanced strategies are developed for the fabrication of atomically precise nanostructured Pt catalysts. This review summarises recent developments in the electrochemical, photochemical and physical deposition techniques for Pt NPs on various supports and their effects on the physicochemical properties and electrocatalytic activity towards the ORR.Financial support by the Estonian Research Council (grant PRG723) and by the EU through the European Regional Development Fund (TK141, “Advanced materials and high-technology devices for energy recuperation systems”) is gratefully acknowledged. G.M. is grateful to CAPES-PrInt (grant 88881.311799/2018e01) for the financial support

Fused Hybrid Linkers for Metal–Organic Frameworks-Derived Bifunctional Oxygen Electrocatalysts

Preparation of electrocatalysts often relies on the use of multiple starting materials – inorganic salts or organometallic precursors, nanostructured carbon supports, organic additives, dopants and carbonization under modifying atmospheres (e.g. NH3 or H2) – with the examples of electrocatalysts arising from a single precursor being much less common. Herein, we have surveyed a series of heterobivalent scaffolds to identify an iron/benzimidazole-based metal– organic framework as a uniform starting material. By merging the catechol and imidazole units together, we get direct entry into a highly efficient bifunctional oxygen electrocatalyst, which alleviates the need for additional dopants and modifying conditions (ORR: Eon = 1.01 V, E1/2 = 0.87 V vs. RHE in 0.1 M KOH; OER: 1.60 V @10 mA cm–2 in 0.1 M KOH; ∆E = 0.73 V). We demonstrate that by fine-tuning the chemical nature of an organic linker, one is able modulate the electrochemical properties of a single precursor-derived electrocatalyst material. </div

Template-Assisted Mechanosynthesis Leading to Benchmark Energy Efficiency and Sustainability in the Production of Bifunctional Fe-N-C Electrocatalysts

Efficient and sustainable synthesis of performant metal/nitrogen-doped carbon (M-N-C) catalysts for oxygen reduction and evolution reactions (ORR/OER) is vital for the global switch to green energy technologies-fuel cells and metal-air batteries. This study reports a solid-phase template-assisted mechanosynthesis of Fe-N-C, featuring low-cost and sustainable FeCl3, 2,4,6-tri(2-pyridyl)-1,3,5-triazine (TPTZ), and NaCl. A NaCl-templated Fe-TPTZ metal-organic material was formed using facile liquid-assisted grinding/compression. With NaCl, the Fe-TPTZ template-induced stability allows for a rapid, thus, energy-efficient pyrolysis. Among the produced materials, 3D-FeNC-LAG exhibits remarkable performance in ORR (E1/2 = 0.85 V and Eonset = 1.00 V), OER (Ej=10 = 1.73 V), and in the zinc-air battery test (power density of 139 mW cm-2). The multilayer stream mapping (MSM) framework is presented as a tool for creating a sustainability assessment protocol for the catalyst production process. MSM employs time, cost, resource, and energy efficiency as technoeconomic sustainability metrics to assess the potential upstream impact. MSM analysis shows that the 3D-FeNC-LAG synthesis exhibits 90% overall process efficiency and 97.67% cost efficiency. The proposed synthetic protocol requires 2 times less processing time and 3 times less energy without compromising the catalyst efficiency, superior to the most advanced methods.Green Open Access added to TU Delft Institutional Repository 'You share, we take care!' - Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.Team Peyman Taher

Template-Assisted Mechanosynthesis Leading to Benchmark Energy Efficiency and Sustainability in the Production of Bifunctional Fe-N-C Electrocatalysts

Efficient and sustainable synthesis of performant metal/nitrogen-doped carbon (M-N-C) catalysts for oxygen reduction and evolution reactions (ORR/OER) is vital for the global switch to green energy technologies-fuel cells and metal-air batteries. This study reports a solid-phase template-assisted mechanosynthesis of Fe-N-C, featuring low-cost and sustainable FeCl3, 2,4,6-tri(2-pyridyl)-1,3,5-triazine (TPTZ), and NaCl. A NaCl-templated Fe-TPTZ metal-organic material was formed using facile liquid-assisted grinding/compression. With NaCl, the Fe-TPTZ template-induced stability allows for a rapid, thus, energy-efficient pyrolysis. Among the produced materials, 3D-FeNC-LAG exhibits remarkable performance in ORR (E1/2 = 0.85 V and Eonset = 1.00 V), OER (Ej=10 = 1.73 V), and in the zinc-air battery test (power density of 139 mW cm-2). The multilayer stream mapping (MSM) framework is presented as a tool for creating a sustainability assessment protocol for the catalyst production process. MSM employs time, cost, resource, and energy efficiency as technoeconomic sustainability metrics to assess the potential upstream impact. MSM analysis shows that the 3D-FeNC-LAG synthesis exhibits 90% overall process efficiency and 97.67% cost efficiency. The proposed synthetic protocol requires 2 times less processing time and 3 times less energy without compromising the catalyst efficiency, superior to the most advanced methods.</p