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Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts

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A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Electrocatalysis".

Deadline for manuscript submissions: closed (31 December 2022) | Viewed by 29141

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Prof. Dr. Vladimir Guterman

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Chemistry Faculty, Southern Federal University, 344090 Rostov-on-Don, Russia
Interests: synthesis, structure and properties of nanostructured electrocatalysts for low-temperature fuel cells (Pt/C, Pt-Me/C, etc.); lithium-metal and lithium-alloy batteries; lithium alloys, intermetallics and multiphase materials behavior; theory and computer modeling of electrochemical nucleation

Dr. Sergey Belenov

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Chemistry Faculty, Southern Federal University, 344090 Rostov-on-Don, Russia
Interests: synthesis, structure, and properties of nanostructured electrocatalysts for low-temperature fuel cells and electrolyzers
Special Issues, Collections and Topics in MDPI journals

Dr. Anastasia Alekseenko

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Dear Colleagues,

New possibilities for mankind and its growing impact on the environment have generated new problems and led to the emergence of advanced scientific and technological areas associated with the development of chemical and electrochemical technologies. Catalysts, among which platinum-containing materials occupy a special place, play an important role in a wide variety of processes. Attempts to create analogous by effectivity platinum-free catalysts have not yet led to convincing practical advances. At the same time, research related to the doping of platinum with some d-metals has received great development. The use of alloying components of various natures, in combination with the formation of a wide range of complex structural types of Pt-M nanoparticles (solid solutions, intermetallic compounds, core-shell, gradient NPs, nano-frames, etc.) made it possible to significantly increase the activity, selectivity, and stability of catalysts in a wide variety of chemical and electrochemical reactions.

This Special Issue, “Pt-M (M = Ni, Co, Cu, etc.)/C Electrocatalysts”, will provide information on new advanced Pt-M catalysts that are promising for use in various chemical, electrochemical, and photochemical processes. We welcome papers devoted to the development of new methods of synthesis and the search for new architectural types of platinum-metal nanoparticles with high catalytic activity, the study of the mechanism of reactions occurring on such catalysts, the analysis of the mechanisms of catalyst degradation, and the search for ways to increase their durability. We encourage the submission of theoretical and experimental papers, and reviews covering all topics related to Pt-M catalysts and their application in a variety of processes and devices.

Prof. Dr. Vladimir Guterman
Dr. Sergey Belenov
Dr. Anastasia Alekseenko
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

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Keywords

Platinum catalysts
Platinum electrocatalysts
Bimetallic catalysts
Platinum alloys
Carbon dioxide conversion
Fuel cells
Hydrogen production
Pt-M nanoparticles

Published Papers (13 papers)

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13 pages, 1893 KiB

Open AccessFeature PaperArticle

PtM/CNT (M = Mo, Ni, CoCr) Electrocatalysts with Reduced Platinum Content for Anodic Hydrogen Oxidation and Cathodic Oxygen Reduction in Alkaline Electrolytes

by Inna Vernigor, Vera Bogdanovskaya, Marina Radina, Vladimir Andreev and Oleg Grafov

Catalysts 2023, 13(1), 161; https://doi.org/10.3390/catal13010161 - 10 Jan 2023

Cited by 4 | Viewed by 1429

Abstract

Bimetallic catalysts containing platinum and transition metals (PtM, M = Mo, Ni, CoCr) were synthesized on carbon nanotubes (CNTs) functionalized in an alkaline medium. Their platinum content is 10–15% by mass. PtM/CNT_NaOH are active in both the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR) in alkaline electrolytes. Although catalysts based on a single transition metal are inactive in the HOR, their activity in the cathode process of ORR increases relative to CNT_NaOH. When using the rotating ring-disk electrode method for ORR, PtM/CNT showed a high selectivity in reducing oxygen directly to water. In HOR, the PtM/CNT catalyst had an activity comparable to that of a commercial monoplatinum catalyst. The results obtained show that it is possible to use the PtM/CNT catalyst in an alkaline fuel cell both as an anode and as a cathode. Full article

(This article belongs to the Special Issue Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts)

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10 pages, 2062 KiB

Open AccessFeature PaperArticle

Pulse Electrolysis Technique for Preparation of Bimetal Tin-Containing Electrocatalytic Materials

by Alexandra Kuriganova, Marina Kubanova, Igor Leontyev, Tatiana Molodtsova and Nina Smirnova

Catalysts 2022, 12(11), 1444; https://doi.org/10.3390/catal12111444 - 15 Nov 2022

Viewed by 1260

Abstract

Platinum–tin-containing materials are the most popular catalysts for processes occurring in fuel cells with direct ethanol oxidation. Pulse electrolysis based on the electrochemical dispersion of platinum electrodes under the influence of alternating pulse current in an alkaline electrolyte made it possible to introduce the tin component into the catalyst in the form of a dopant, an alloy with platinum, and in the form of an oxide phase and evaluate the effect of the form in which tin is present in the catalyst on its microstructural and electrocatalytic characteristics. The introduction of tin into the catalyst generally increases the rate of ethanol electrooxidation; however, with the most prominent effect observed when tin is present in form of an oxide. Full article

(This article belongs to the Special Issue Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts)

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12 pages, 2941 KiB

Open AccessFeature PaperArticle

Superior Performance of an Iron-Platinum/Vulcan Carbon Fuel Cell Catalyst

by Prabal Sapkota, Sean Lim and Kondo-Francois Aguey-Zinsou

Catalysts 2022, 12(11), 1369; https://doi.org/10.3390/catal12111369 - 4 Nov 2022

Cited by 4 | Viewed by 1748

Abstract

This work reports on the synthesis of iron-platinum on Vulcan carbon (FePt/VC) as an effective catalyst for the electrooxidation of molecular hydrogen at the anode, and electroreduction of molecular oxygen at the cathode of a proton exchange membrane fuel cell. The catalyst was synthesized by using the simple polyol route and characterized by XRD and HRTEM along with EDS. The catalyst demonstrated superior electrocatalytic activity for the oxygen reduction reaction and the oxidation of hydrogen with a 2.4- and 1.2-fold increase compared to platinum on Vulcan carbon (Pt/VC), respectively. Successful application of FePt/VC catalyst in a self-breathing fuel cell also showed a 1.7-fold increase in maximum power density compared to Pt/VC. Further analysis by accelerated stress test demonstrated the superior stability of FePt on the VC substrate with a 4% performance degradation after 60,000 cycles. In comparison, a degradation of 6% after 10,000 cycles has been reported for Pt/Ketjenblack. Full article

(This article belongs to the Special Issue Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts)

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14 pages, 2741 KiB

Open AccessArticle

The Development of High-Performance Platinum-Ruthenium Catalysts for the Methanol Oxidation Reaction: Gram-Scale Synthesis, Composition, Morphology, and Functional Characteristics

by Vladislav Menshikov, Kirill Paperzh, Yulia Bayan, Yegor Beskopylny, Aleksey Nikulin, Ilya Pankov and Sergey Belenov

Catalysts 2022, 12(10), 1257; https://doi.org/10.3390/catal12101257 - 17 Oct 2022

Cited by 3 | Viewed by 2190

Abstract

To obtain the PtRu/C electrocatalysts, the surfactant-free (wet) synthesis methods have been used. The structural-morphological characteristics and electrochemical behavior of the catalysts have been studied. The possibility of ranging the crystallite size from 1.2 to 4.5 nm using different reducing agents (ethylene glycol, ethanol, and isopropanol) has been shown. The effect of both the particles’ size and the mass fraction of the metal component on the electrochemical surface area (ESA), activity in the methanol electrooxidation reaction (MOR), and tolerance to its intermediate products has been studied. The simple and scalable surfactant-free synthesis method of the highly active PtRu/C electrocatalysts with a different mass fraction of metals, with their tolerance to intermediate products of the oxidation being 2.3 times higher than the commercial analogue, has been first proposed. The authors have succeeded in obtaining the PtRu/C catalysts with the nanoparticles’ size of less than 2 nm, characterized by the ultranarrow size and uniform spatial distributions over the support surface, thus having the ESA of more than 90 m²g_PtRu⁻¹. Full article

(This article belongs to the Special Issue Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts)

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16 pages, 4806 KiB

Open AccessFeature PaperArticle

Role of the Potential Range during Stress Testing of Platinum-Containing Electrocatalysts at Elevated Temperature

by Irina Gerasimova, Sergey Belenov, Nikolai Lyanguzov, Ilya Pankov, Mikhail Tolstunov and Angelina Pavlets

Catalysts 2022, 12(10), 1179; https://doi.org/10.3390/catal12101179 - 6 Oct 2022

Cited by 5 | Viewed by 1664

Abstract

The durability of low temperature proton exchange membrane fuel cell (PEMFC) catalysts crucially affects their lifetime. The choice of carbon support is important in terms of increasing the stability of catalysts. In this research, Pt/C samples were obtained using the polyol synthesis method on two types of carbon supports: the standard support, Vulcan XC-72, and carbon support with a high degree of graphitization, ECS-002402. One method for assessing structural characteristics is through transmission electron microscopy (TEM), according to which materials G1 and G2 showed an average nanoparticle size of 3.7 and 4.2 nm, respectively. On all catalysts, the oxygen reduction reaction proceeded according to the four electron mechanism. Durability was assessed by changes in ESA and activity in the ORR after 1000 cycles, with changes in the upper potential values: 0.7; 1.0; 1.2; and 1.4 V. After accelerated stress testing, the G1 material showed the greatest residual activity at a potential of 1.4 V (165 A/g (Pt). Based on the results of comparing various ADT protocols, the optimal mode of 0.4 and 1.4 V was chosen, and should be used for further studies comparing the durability of Pt/C catalysts. Full article

(This article belongs to the Special Issue Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts)

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10 pages, 1731 KiB

Open AccessArticle

Enhancement on PrBa_0.5Sr_0.5Co_1.5Fe_0.5O₅ Electrocatalyst Performance in the Application of Zn-Air Battery

by Chengcheng Wang, Ziheng Zheng, Zian Chen, Xinlei Luo, Bingxue Hou, Mortaza Gholizadeh, Xiang Gao, Xincan Fan and Zanxiong Tan

Catalysts 2022, 12(7), 800; https://doi.org/10.3390/catal12070800 - 20 Jul 2022

Cited by 4 | Viewed by 1543

Abstract

Due to the insufficient stability and expensive price of commercial precious metal catalysts like Pt/C and IrO₂, it is critical to study efficiently, stable oxygen reduction reaction as well as oxygen evolution reaction (ORR/OER) electrocatalysts of rechargeable Zn-air batteries. PrBa_0.5Sr_0.5Co_1.5Fe_0.5O₅ (PBSCF) double perovskite was adopted due to its flexible electronic structure as well as higher electro catalytic activity. In this study, PBSCF was prepared by the citrate-EDTA method and the optimized amount of PBSCF-Pt/C composite was used as a potential ORR/OER bifunctional electrocatalyst in 0.1 M KOH. The optimized composite exhibited excellent OER intrinsic activity with an onset potential of 1.6 V and Tafel slope of 76 mV/dec under O₂-saturated 0.1 M KOH. It also exhibited relatively competitive ORR activity with an onset potential of 0.9 V and half-wave potential of 0.78 V. Additionally, Zn–air battery with PBSCF composite catalyst showed relatively good stability. All these results illustrate that PBSCF-Pt/C composite is a promising bifunctional electrocatalyst for rechargeable Zn-air batteries. Full article

(This article belongs to the Special Issue Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts)

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8 pages, 2954 KiB

Open AccessArticle

An Efficient Electrocatalyst (PtCo/C) for the Oxygen Reduction Reaction

by Bingxue Hou, Xinlei Luo, Ziheng Zheng, Rui Tang, Qi Zhang, Mortaza Gholizadeh, Chengcheng Wang and Zanxiong Tan

Catalysts 2022, 12(7), 794; https://doi.org/10.3390/catal12070794 - 19 Jul 2022

Cited by 3 | Viewed by 2234

Abstract

The oxygen reduction reaction (ORR) is paid much more attention because of the high overpotential required for driving the four-electron process in the field of storage and sustainable energy conversion, including fuel cell applications. In this paper, PtCo nanoparticles encapsulated on carbon supports were prepared by a simple modified polyol method with ethylene glycol. Structural as well as electrochemical characterizations illustrated that the PtCo/C electrocatalysts had a minimum particle size of 4.8 nm, which is close to the commercial 40 wt% Pt/JM. Moreover, the electrochemical measurements indicated that ORR activity was competitive with the commercial 40 wt% Pt/JM catalyst. The synthesis method is a critical way to produce PtCo/C catalysts for use in polymer electrolyte membranes in fuel cells (PEMFCs). Full article

(This article belongs to the Special Issue Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts)

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14 pages, 3449 KiB

Open AccessArticle

Platinum-Containing Nanoparticles on N-Doped Carbon Supports as an Advanced Electrocatalyst for the Oxygen Reduction Reaction

by Anastasia Alekseenko, Angelina Pavlets, Elizaveta Moguchikh, Mikhail Tolstunov, Evgeny Gribov, Sergey Belenov and Vladimir Guterman

Catalysts 2022, 12(4), 414; https://doi.org/10.3390/catal12040414 - 7 Apr 2022

Cited by 7 | Viewed by 2655

Abstract

New highly active electrocatalysts were obtained by depositing bimetallic Pt-Cu nanoparticles on the surface of an N-doped carbon support. The structural–morphological characteristics and electrochemical behavior of the catalysts were studied. Using current stress testing protocols, their resistance to degradation was assessed in comparison with that of a commercial Pt/C material. A combined approach to catalyst synthesis that consists in alloying platinum with copper and doping the support makes it possible to obtain catalysts with a uniform distribution of bimetallic nanoparticles on the carbon surface. The obtained catalysts exhibit high activity and durability. Full article

(This article belongs to the Special Issue Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts)

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19 pages, 5780 KiB

Open AccessFeature PaperArticle

Gram-Scale Synthesis of CoO/C as Base for PtCo/C High-Performance Catalysts for the Oxygen Reduction Reaction

by Dmitry Mauer, Sergey Belenov, Vladimir Guterman, Anatoly Nikolsky, Alexey Kozakov, Alexey Nikulin, Danil Alexeenko and Olga Safronenko

Catalysts 2021, 11(12), 1539; https://doi.org/10.3390/catal11121539 - 17 Dec 2021

Cited by 5 | Viewed by 2564

Abstract

The composition, structure, catalytic activity in the ORR and stability of PtCo/C materials, obtained in two stages and compared with commercial Pt/C analogs, were studied. At the first stage of the synthesis performed by electrodeposition of cobalt on a carbon support, a CoO_x/C composite containing 8% and 25 wt% cobalt oxide was successfully obtained. In the second step, PtCoO_x/C catalysts of Pt1.56Co and Pt1.12Co composition containing 14 and 30 wt% Pt, respectively, were synthesized based on the previously obtained composites. According to the results of the composition and structure analysis of the obtained PtCoO_x/C catalysts by X-ray diffraction (XRD), X-ray fluorescence analysis (XRF), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) methods, the formation of small bimetallic nanoparticles on the carbon support surface has been proved. The resulting catalysts demonstrated up to two times higher specific catalytic activity in the ORR and high stability compared to commercial Pt/C analogs. Full article

(This article belongs to the Special Issue Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts)

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13 pages, 2291 KiB

Open AccessArticle

Influence of PtCu/C Catalysts Composition on Electrochemical Characteristics of Polymer Electrolyte Fuel Cell and Properties of Proton Exchange Membrane

by Irina Falina, Angelina Pavlets, Anastasia Alekseenko, Ekaterina Titskaya and Natalia Kononenko

Catalysts 2021, 11(9), 1063; https://doi.org/10.3390/catal11091063 - 31 Aug 2021

Cited by 9 | Viewed by 2208

Abstract

The present work aimed to investigate the influence of “weakly bound“ copper dissolution from the surface of bimetallic PtCu_x/C catalysts on the properties of proton exchange membrane and the membrane electrode assembly (MEA) in general. A number of PtCu_x/C materials have been obtained by the simultaneous reduction in copper and platinum precursors in the course of liquid-phase synthesis with a varying ratio of metals from PtCu_2.0/C to PtCu_0.3/C. All bimetallic PtCu_x/C electrocatalysts after the activation stage exhibit high activity in the oxygen electroreduction reaction. The PtCu_x/C catalysts in “as prepared” state were tested in MEA. The increase in Cu content in PtCu_x/C catalysts led to a decrease in current density of MEA while its resistance was almost independent of the Cu fraction in the catalyst. The membrane saturation degree by Cu²⁺-ions after MEA testing did not exceed 40%, even in the case of the PtCu_2.0/C material. The main reason for the degradation of membrane electrode assembly with PtCu_x/C materials is the transport limitation caused by the contamination of Nafion in three catalytic layer by “weakly bound” copper ions. Full article

(This article belongs to the Special Issue Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts)

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20 pages, 4053 KiB

Open AccessFeature PaperArticle

Testing PtCu Nanoparticles Supported on Highly Ordered Mesoporous Carbons CMK3 and CMK8 as Catalysts for Low-Temperature Fuel Cells

by Julia Garcia-Cardona, Francisco Alcaide, Enric Brillas, Ignasi Sirés and Pere L. Cabot

Catalysts 2021, 11(6), 724; https://doi.org/10.3390/catal11060724 - 10 Jun 2021

Cited by 10 | Viewed by 2425

Abstract

Pt(Cu) nanoparticles supported on CMK3 and CMK8 ordered mesoporous carbons (OMCs) have been synthesized by electroless deposition of Cu followed by galvanic exchange with Pt. The structural characterization by high-resolution transmission electron microscopy and X-ray diffraction showed the formation of Pt(Cu) nanoparticles of 4–5 nm, in which PtCu alloys with contracted fcc Pt lattice and 70–80 at.% Pt was identified. The X-ray photoelectron spectroscopy analyses indicated that the Pt(Cu) nanoparticles were mainly composed of a PtCu alloy core covered by a Pt-rich shell, in agreement with the steady cyclic voltammograms, which did not show any Cu oxidation peaks. Electroactive surface areas up to about 70 m² g_Pt⁻¹ were obtained. The onset potentials for CO oxidation and the oxygen reduction reaction were more negative and positive, respectively, as compared to Pt/C, thus indicating higher activity of these Pt(Cu) catalysts with respect to the latter. Based on the corresponding binding energies, these better activities were attributed to the favorable geometric and ligand effects of Cu on Pt, which were able to reduce the adsorption energy of the intermediates on Pt. Pt(Cu)/CMK3 showed competitive mass and specific activities, as well as better stability than Pt/C. Full article

(This article belongs to the Special Issue Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts)

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18 pages, 5263 KiB

Open AccessFeature PaperArticle

Methanol, Ethanol, and Formic Acid Oxidation on New Platinum-Containing Catalysts

by Vladislav S. Menshikov, Ivan N. Novomlinsky, Sergey V. Belenov, Anastasya A. Alekseenko, Olga I. Safronenko and Vladimir E. Guterman

Catalysts 2021, 11(2), 158; https://doi.org/10.3390/catal11020158 - 23 Jan 2021

Cited by 18 | Viewed by 3342

Abstract

Electrooxidation of methanol, ethanol, and formic acid was studied on three platinum-containing electrocatalysts: PtCu/C, Pt/(SnO₂/C), and Pt/C, Pt content being about 20 wt%. In all reactions, the integral specific activity of the catalysts, estimated from the results of cyclic voltammetry, grows in the Pt/C < Pt/(SnO₂/C) < PtCu/C row. The influence of the reagent nature subjected to electrooxidation is manifested both in the difference of the absolute rate values of the corresponding reactions, decreasing in the order CH₃OH > HCOOH > C₂H₅OH, and in the different ratio of these rates on different catalysts and at different potentials. Pt/(SnO₂/C) catalyst containing SnO₂ nanoparticles is the most active among the studied catalysts in methanol and formic acid electrooxidation reactions under potentiostatic conditions at the E = 0.60 V. Moreover, in formic acid electrooxidation reaction it is significantly superior to even the PtRu/C commercial catalyst. The reasons for the positive influence of Cu atoms and SnO₂ nanoparticles on the catalytic activity of platinum are presumably associated with different effects: Interaction of the d-orbitals of copper and platinum atoms in bimetallic nanoparticles and implementation of the bifunctional catalysis mechanism on the adjacent platinum and tin dioxide nanoparticles. Full article

(This article belongs to the Special Issue Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts)

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Review

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29 pages, 5345 KiB

Open AccessReview

Architecture Evolution of Different Nanoparticles Types: Relationship between the Structure and Functional Properties of Catalysts for PEMFC

by Sergey Belenov, Anastasia Alekseenko, Angelina Pavlets, Alina Nevelskaya and Maria Danilenko

Catalysts 2022, 12(6), 638; https://doi.org/10.3390/catal12060638 - 10 Jun 2022

Cited by 8 | Viewed by 2247

Abstract

This review considers the features of the catalysts with different nanoparticle structures architecture transformation under the various pre-treatment types. Based on the results of the publications analysis, it can be concluded that the chemical or electrochemical activation of bimetallic catalysts has a significant effect on their composition, microstructure, and catalytic activity in the oxygen reduction reaction. The stage of electrochemical activation is recommended for use as a mandatory catalyst pre-treatment to obtain highly active de-alloyed materials. The literature is studied, which covers possible variants of the structural modification under the influence of thermal treatment under different processing conditions. Additionally, based on the literature data analysis, recommendations are given for the thermal treatment of catalysts alloyed with various d-metals. Full article

(This article belongs to the Special Issue Pt-M (M = Ni,Co,Cu, etc.)/C Electrocatalysts)

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