High-temperature treatment to engineer the single-atom Pt coordination environment towards highly efficient hydrogen evolution

Chen, Shanyong; Lv, Changchang; Liu, Ling; Li, Muhong; Liu, Jian; Ma, Jinyang; Hao, Panpan; Wang, Xuan; Ding, Weiping; Xie, Mingjiang; Guo, Xuefeng

doi:10.1016/j.jechem.2020.11.004

Cited by 27 publications

(9 citation statements)

References 56 publications

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“…In 2020, the first highly active Metal-N-C material based on a p-block metal, namely Sn, was reported, with Sn-Nx sites having similar TOF for ORR in acid medium than Fe-Nx sites [91]. However, the material contained also SnOx nanoclusters, in addition to recently with various synthetic routes but that are similar to those established previously for Fe-N-C, for example for Pt [92], rhodium [93]. Pt-Nx sites in Pt-N-C have been found to efficiently catalyse the HER, with the advantage of increased utilization of expensive PGM, compared to PGM NP, where less than 100 % of the metal is on the surface.…”

Section: Synthesis Of Metal-n-c Smac Beyond Fe and Cosupporting

confidence: 62%

Electrocatalysis with Single‐Metal Atom Sites in Doped Carbon Matrices

Asset¹,

Maillard²,

Jaouen³

2022

Supported Metal Single Atom Catalysis

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While supported metal nanoparticles cannot achieve full electrochemical utilisation of metal atoms, catalysts featuring single metal atom sites may offer this possibility, along with advantages in selectivity. However, the passage from nanometric to atomic dimension is not without consequences. It first raises the question of efficient and robust synthesis methods, and underlines the need of cutting-edge characterization techniques that can target single metal atoms. These analytical tools are also pivotal to gain insights into the structure of the active sites, and establish atomic structure-catalytic activity-selectivity-stability relationships. Herein, we illustrate these topics for electrocatalysis, with a particular focus on metal-nitrogen-carbon single metal atom catalysts, for which a fantastic leap forward has been achieved in the last 15 years, triggered by the growing interest in sustainable energy storage and conversion systems.C SMAC prepared via pyrolysis in the following decades. Hence, we focus mainly on the synthesis methods of Fe-and Co-N-C SMAC in this section. While in those early days, the use of Metal-N4 macrocycles without pyrolysis secured the well-defined Metal-N4 active centres, the different approaches used to interface them with a conductive support impacted the local environment of metal cations and their accessibility. Phthalocyanines and porphyrins are poorly soluble in water, and different solvents or suspensions in concentrated sulphuric acid were used, removing the solvent by evaporation or precipitating the macrocycle on the support. The dispersion quality of metal macrocycles on supports were shown to depend strongly on the morphology, specific surface area (SSA) but also on acido-basic properties of carbon supports [17,18]. For example, the characterization by 57 Fe Mössbauer spectroscopy, a technique which allows identifying the different coordinations and spin states of Fe (discussed in more detail in 13.3), of iron phthalocyanine (Fe-Pc) precipitated on a carbon powder revealed multiple coordinations and spin states for Fe, whereas a single coordination and electronic state was seen for the Fe-Pc monomer [17]. Controlled deposition or solvent removal however resulted in Fe-Pc/C composites with a single (or vast majority of one) 57 Fe Mössbauer spectroscopic signature [19]. For example, removal of the pyridine solvent for Fe-Pc by boiling it off at 420 °C resulted in a Fe-Pc/C composite with 95 % of the spectral signal assigned to one specific doublet [19]. The latter can nowadays be assigned to an O2-Fe(III)-N4 coordination [20], implying high dispersion and accessibility to O2 of the Fe-N4 sites.While some heterogeneities of metal coordination and site accessibility were exemplified above for SMAC prepared via interfacing Metal-N4 macrocycles without high-temperature pyrolysis, the extent of heterogeneities was progressively increased, and the true nature of the active site blurred for several decades, with the introduction of high-temperature treatments of macrocycles in a...

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Section: Synthesis Of Metal-n-c Smac Beyond Fe and Cosupporting

confidence: 62%

Electrocatalysis with Single‐Metal Atom Sites in Doped Carbon Matrices

Asset¹,

Maillard²,

Jaouen³

2022

Supported Metal Single Atom Catalysis

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“…Moreover, this outstanding performance makes Pt edge‐doped MoS 2 one of the top HER catalysts among the previously reported Pt‐based catalysts (Figure 5d and Table S3, Supporting Information). [ 5,6,9–12,16,27,46 ] The geometry information of commercial Pt/C is demonstrated by TEM image shown in Figure S18 (Supporting Information). It can be verified that the Pt particles in commercial Pt/C are no larger than edge‐doped Pt, which are approximately less than 4 nm, confirming that size could not be the reason for the superiority of Pt edge‐doped MoS 2 .…”

Section: Resultsmentioning

confidence: 99%

“…[ 5–8 ] Therefore, numerous efforts have been devoted to improving the mass activity and stability of Pt catalysts. [ 9–14 ] The development of hybrid electrocatalysts, which combine Pt with non‐noble catalysts, is a promising solution to this problem. [ 15–18 ]…”

Section: Introductionmentioning

confidence: 99%

Pt Edge‐Doped MoS₂: Activating the Active Sites for Maximized Hydrogen Evolution Reaction Performance

Pei

Qiao

Chen

et al. 2021

Small

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The demand of clean energy calls for efficient and low‐cost hydrogen evolution reaction electrocatalysts. Fabricating hybrid catalysts from noble/non‐noble catalysts is a practical route to reducing the consumption of noble metals and enhancing catalytic efficiency. Here, 2H‐MoS2 is etched and edge‐doped with Pt nanoparticles using focused ion beam and photoreduction techniques. Precise comparison of as‐prepared samples demonstrates that the enhancement of catalytic performance can be controlled through tuning the catalyst defect length. On this basis, remarkably high performance is obtained by designing a specific defect array that is superior to commercial Pt/C with less Pt loading and higher mass activity. It has been proved by experimentation and COMSOL Multiphysics simulations that the promotion of catalytic activity not only benefits from the synergistic effect of Pt and edge active sites, but also contributes to the increased potential at the edges of the designed defect. This study sheds light on the mechanism of understanding nanoscale edge‐doped hybrid catalysts and provides a feasible strategy for the full utilization of noble metals.

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“…In the early stage, metal-oxide photocatalysts (such as TiO 2 , Bi 2 O 3 , and ZnO) were used to produce hydrogen in the photocatalytic process. 7,8 Then, g-C 3 N 4 was paid more attention by researchers due to its excellent photochemical stability and unique optical properties. However, these photocatalysts have some limitations, such as a high recombination ratio of photogenerated electrons and holes and weak visible-light absorption.…”

Section: Introductionmentioning

confidence: 99%

“…Hydrogen, as clean renewable energy with high energy density, has attracted widespread attention. − It is expected that photocatalytic hydrogen production will be a prospective and promising way to solve energy and environmental problems. , In the past few decades, many researchers have made extensive efforts to develop various efficient photocatalysts. In the early stage, metal-oxide photocatalysts (such as TiO 2 , Bi 2 O 3 , and ZnO) were used to produce hydrogen in the photocatalytic process. , Then, g-C 3 N 4 was paid more attention by researchers due to its excellent photochemical stability and unique optical properties. However, these photocatalysts have some limitations, such as a high recombination ratio of photogenerated electrons and holes and weak visible-light absorption.…”

Section: Introductionmentioning

confidence: 99%

Ti₃C₂ Quantum Dots Modified 3D/2D TiO₂/g-C₃N₄ S-Scheme Heterostructures for Highly Efficient Photocatalytic Hydrogen Evolution

Dong

Zhang

Wang

et al. 2021

ACS Appl. Energy Mater.

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Photocatalytic hydrogen production is a promising technology to alleviate the problems of energy shortage and environmental pollution faced by human society. In this paper, the S-scheme heterojunction TiO 2 /g-C 3 N 4 was modified by Ti 3 C 2 quantum dots (QDs) to prepare a three-dimensional/two-dimensional/zero-dimensional (3D/2D/0D) photocatalyst for photocatalytic hydrogen production. The S-scheme heterojunction structure reduces the recombination rate of photogenerated electron−hole pairs and produces more photogenerated electrons. At the same time, Ti 3 C 2 quantum dots as electron acceptors improve the ability to capture transition electrons, obtain more photogenerated carriers involved in surface reactions, and increase the number of active sites. The TiO 2 /g-C 3 N 4 /Ti 3 C 2 QDs composite catalyst shows excellent photocatalytic hydrogen evolution performance under visible light due to its unique structure and optical properties. The photocatalytic hydrogen production rate reached the maxima of 5540.21 μmol•h −1 g −1 , which is nearly 2 times higher than the production rates observed for TiO 2 /g-C 3 N 4 . The structure of 3D/2D/0D TiO 2 /g-C 3 N 4 /Ti 3 C 2 QDs was constructed, and the electron transfer path was verified by transient absorption spectroscopy and density functional theory calculation. KEYWORDS: TiO 2 /g-C 3 N 4 composites, Ti 3 C 2 quantum dots, S-scheme heterojunction, photocatalytic hydrogen production, DFT calculation

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High-temperature treatment to engineer the single-atom Pt coordination environment towards highly efficient hydrogen evolution

Cited by 27 publications

References 56 publications

Electrocatalysis with Single‐Metal Atom Sites in Doped Carbon Matrices

Electrocatalysis with Single‐Metal Atom Sites in Doped Carbon Matrices

Pt Edge‐Doped MoS₂: Activating the Active Sites for Maximized Hydrogen Evolution Reaction Performance

Ti₃C₂ Quantum Dots Modified 3D/2D TiO₂/g-C₃N₄ S-Scheme Heterostructures for Highly Efficient Photocatalytic Hydrogen Evolution

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High-temperature treatment to engineer the single-atom Pt coordination environment towards highly efficient hydrogen evolution

Cited by 27 publications

References 56 publications

Electrocatalysis with Single‐Metal Atom Sites in Doped Carbon Matrices

Electrocatalysis with Single‐Metal Atom Sites in Doped Carbon Matrices

Pt Edge‐Doped MoS2: Activating the Active Sites for Maximized Hydrogen Evolution Reaction Performance

Ti3C2 Quantum Dots Modified 3D/2D TiO2/g-C3N4 S-Scheme Heterostructures for Highly Efficient Photocatalytic Hydrogen Evolution

Contact Info

Product

Resources

About

Pt Edge‐Doped MoS₂: Activating the Active Sites for Maximized Hydrogen Evolution Reaction Performance

Ti₃C₂ Quantum Dots Modified 3D/2D TiO₂/g-C₃N₄ S-Scheme Heterostructures for Highly Efficient Photocatalytic Hydrogen Evolution