Plasmonic Au nanoclusters dispersed in nitrogen-doped graphene as a robust photocatalyst for light-to-hydrogen conversion

Dao, Dung Van; Cipriano, Luis A.; Liberto, Giovanni Di; Nguyen, Thuy Ngoc; Ki, Sang-Woo; Son, Hyungbin; Kim, Gyu-Cheol; Lee, Kang Hyun; Yang, Jin-Kyu; Yu, Yeon–Tae; Pacchioni, Gianfranco; Lee, In-Hwan

doi:10.1039/d1ta05445g

Cited by 33 publications

(20 citation statements)

References 48 publications

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“…This is because an extended Au surface binds hydrogen too weakly (Δ G H > 0) and a Au atom too strongly (Δ G H < 0). On Au nanoclusters, on the contrary, the H adsorption free energy is neither too positive nor too negative and results in a higher activity . However, there is clear evidence from the experiments that plasmonic effects also play an important role in capturing the visible light, an effect connected to the size and shape of Au nanoclusters that adds to their intrinsically higher activity.…”

Section: Sacs Supported Clusters and Homogeneous Catalystsmentioning

confidence: 97%

“…The HER has been investigated with three catalysts based on Au deposited on nitrogen-doped graphene (N-Gr) . The three catalysts, Au single atoms, Au nanoclusters of 0.5–1.0 nm in size, and Au nanoparticles of 20 nm, were prepared by wet chemistry methods and fully characterized at the atomistic level.…”

Section: Sacs Supported Clusters and Homogeneous Catalystsmentioning

confidence: 99%

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A Few Questions about Single-Atom Catalysts: When Modeling Helps

et al. 2022

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Metrics & MoreArticle Recommendations CONSPECTUS: Single-atom catalysis (SAC) is a fascinating and rapidly growing field in heterogeneous catalysis. In less than 20 years, this has become one of the most widely investigated subjects by the catalytic community for various good reasons: the ability to synthesize active catalysts using a minimum amount of precious metals, the expected higher selectivity of SACs compared to assemblies of nanoparticles of variable sizes, and the fact that SACs represent a bridge between homogeneous and heterogeneous catalysis. The relative simplicity of SAC structures compared to classical heterogeneous catalysts based on supported metal nanoparticles has stimulated an intense simulation activity aimed at predicting new potential catalysts from first principles, often based on machine learning algorithms. This is a very ambitious objective and ultimately represents the final goal of every modeling activity: the possibility to provide realistic predictions of new material properties and catalytic reactivity. However, one of the main reasons that theory is useful is and remains the interpretation and analysis of experimental results, with the no less crucial goal of understanding the basic principles that determine a certain functionality or reactivity. The combination of advanced characterization techniques and theoretical calculations can provide a general conceptual framework to better understand structure−function relationships. In this Account, we will address this aspect in trying to provide answers to some fundamental questions related to the structure, stability, and activity of SACs. We will start by addressing a question that arises every time a new SAC is synthesized: where are the metal atoms? What is their coordination mode with the support? Once we have shown how to address this point, we will move on to the next fundamental question: do the single atoms stay put? How does the chemical environment of a SAC depend on the preparation or reaction conditions? Next, we will analyze the importance of a full characterization of the reaction mechanism to predict reactivity. SACs, due to their analogy to coordination compounds, can form intermediates that do not exist on the surface of metal electrodes. The formation of these intermediates can influence the kinetics of the process and must be considered in the simulation. Finally, we will briefly address a more general question: how does the catalytic activity of SACs compare with that of the corresponding supported metal nanoparticles on the one hand or homogeneous molecular complexes on the other? The final message is that to answer these questions and to take full advantage of quantum chemical modeling, the results of the calculations should be continuously verified with experimental data in a cross-fertilization that is beneficial for both sides.

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Section: Sacs Supported Clusters and Homogeneous Catalystsmentioning

confidence: 97%

Section: Sacs Supported Clusters and Homogeneous Catalystsmentioning

confidence: 99%

A Few Questions about Single-Atom Catalysts: When Modeling Helps

et al. 2022

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“…We considered a nitrogen-doped graphene layer where a C divacancy has been created, four C atoms have been replaced by four N atoms, and a TM atom has been embedded in this coordination site, TM@4N-Gr (pyridine coordination). The supercell of 4N-Gr contains 32 atoms and has lattice parameters a , b , and γ equal to 9.87 Å, 9.87 Å, and 120°, respectively. , The atomic coordinates have been fully relaxed for each of the SACs considered.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Metal single atoms stably anchored on a support are among the most studied alternatives to extended metal surfaces for water splitting. ,− Single-atom catalysts (SACs) are the bridge between heterogeneous and homogeneous catalysis, making it possible to fully exploit the amount of catalytic sites. − Furthermore, the chemistry of a metal single atom differs from that of a bulk metal , and can be tailored by engineering the local coordination, opening in principle several possibilities to improve the catalytic activity. The chemistry of SACs is usually complex and reminiscent of that of coordination chemistry compounds.…”

Section: Introductionmentioning

confidence: 99%

Superoxo and Peroxo Complexes on Single-Atom Catalysts: Impact on the Oxygen Evolution Reaction

2022

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In this work, we demonstrate the essential role of the formation of superoxo and peroxo complexes on single-atom catalysts (SACs), an aspect that is often neglected in the study of these systems. By means of density functional theory calculations, we consider a representative set of 11 transition metal atoms (Sc, V, Ti, Cr, Mn, Fe, Co, Ni, Cu, Pd, Pt) anchored on nitrogen-doped graphene, and we show that most of them form stable superoxo and peroxo intermediates when they react with molecular oxygen. Their formation has a direct impact on the oxygen evolution reaction (OER), and we develop the corresponding microkinetic models showing that this step of the reaction cannot be neglected. Depending on the transition metal atom, the inclusion of the superoxo/peroxo complexes in the analysis of the reaction profile can change the kinetics by several orders of magnitude. This work reveals the important role of dioxygen complexes species in the OER and reinforces the notion of SACs as analogs of coordination compounds.

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“…The successful preparation of atomic thin graphene and exploration of its intrinsic properties extensively boost the research of two-dimensional (2D) materials ( Novoselov et al., 2004 ). The large surface area, mechanical, optical, and electronic properties make the 2D materials, such as graphene, MoS 2 , BN, C 3 N 4 and so forth, promising in the field of photocatalysis, electrocatalysis, single-atom catalysis, energy storage, sensors, and optoelectronics ( Feng et al., 2011 ; Liang et al., 2017 ; Mishra et al., 2019 ; Tang and Jiang, 2016 ; Van Dao et al., 2021 ; Wang et al., 2017b ; Zhang, 2015 ; Zhi et al., 2009 ; Zhu et al., 2011 ). III-V semiconductors with exotic structures, direct band gap and high carrier mobility have great potential in manufacturing solar cells, lasers, photodetectors, light-emitting diodes, and other devices, which have attracted tremendous attention in 2D materials ( Chen et al., 2016 ; Cipriano et al., 2020 ; del Alamo, 2011 ; Kobayashi et al., 2012 ; Wallentin et al., 2013 ; Zhang et al., 2019 ).…”

Section: Introductionmentioning

confidence: 99%

Infinite possibilities of ultrathin III-V semiconductors: Starting from synthesis

Wang

Zeng

et al. 2022

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Plasmonic Au nanoclusters dispersed in nitrogen-doped graphene as a robust photocatalyst for light-to-hydrogen conversion

Abstract: Au nanoclusters (2.18 wt%) consisting of a few tens of atoms supported nitrogen-doped graphene deliver an impressive hydrogen evolution reaction rate of 3.16 μmol mgcat−1 h−1 under visible-light irradiation and a high maximum quantum yield of 14.3%.

Cited by 33 publications

References 48 publications

A Few Questions about Single-Atom Catalysts: When Modeling Helps

A Few Questions about Single-Atom Catalysts: When Modeling Helps

Superoxo and Peroxo Complexes on Single-Atom Catalysts: Impact on the Oxygen Evolution Reaction

Infinite possibilities of ultrathin III-V semiconductors: Starting from synthesis

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