DFT calculations for single-atom confinement effects of noble metals on monolayer g-C<sub>3</sub>N<sub>4</sub> for photocatalytic applications

Cheng, Yang; Zhao, Zong‐Yan; Wei, Hongping; Deng, Xiyu; Liu, Qingju

doi:10.1039/d0ra09815a

Cited by 41 publications

(22 citation statements)

References 69 publications

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“…7.3 Å, respectively. ,, The dimension of Ni NPs was shown to be <1 nm, indicating possible Ni insertion and NP stabilization within the CN cavity, as was suggested before . A similar effect was observed for Pd and Pt atoms deposited on g-C 3 N 4 . The 6-fold cavity of g-C 3 N 4 was estimated by DFT calculation to stabilize Pd and Pt atoms, and the binding energies were given as −2.17 and −2.95 eV, respectively.…”

Section: Resultssupporting

confidence: 67%

“… 38 A similar effect was observed for Pd and Pt atoms deposited on g-C 3 N 4 . 47 The 6-fold cavity of g-C 3 N 4 was estimated by DFT calculation to stabilize Pd and Pt atoms, and the binding energies were given as −2.17 and −2.95 eV, respectively. Furthermore, it was shown and evidenced by STM microscopy that, very similar in chemical structure to CN, the porphyrin cavity (i.e., comprising N, C and H), although smaller in dimensions compared to the CN cavity, was able to stabilize Ni and Co. 30 However, within the CN cavity, atoms such as V, Cr, Mn, and Fe were shown to be more stable than their bulk phases.…”

Section: Resultsmentioning

confidence: 99%

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Developing Benign Ni/g-C₃N₄ Catalysts for CO₂ Hydrogenation: Activity and Toxicity Study

Pieta

Gieroba

Kalisz

et al. 2022

Ind. Eng. Chem. Res.

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This research discusses the CO 2 valorization via hydrogenation over the non-noble metal clusters of Ni and Cu supported on graphitic carbon nitride (g-C 3 N 4 ). The Ni and Cu catalysts were characterized by conventional techniques including XRD, AFM, ATR, Raman imaging, and TPR and were tested via the hydrogenation of CO 2 at 1 bar. The transition-metal-based catalyst designed with atom-economy principles presents stable activity and good conversions for the studied processes. At 1 bar, the rise in operating temperature during CO 2 hydrogenation increases the CO 2 conversion and the selectivity for CO and decreases the selectivity for methanol on Cu/CN catalysts. For the Ni/CN catalyst, the selectivity to light hydrocarbons, such as CH 4 , also increased with rising temperature. At 623 K, the conversion attained ca. 20%, with CH 4 being the primary product of the reaction (CH 4 yield >80%). Above 700 K, the Ni/CN activity increases, reaching almost equilibrium values, although the Ni loading in Ni/CN is lower by more than 90% compared to the reference NiREF catalyst. The presented data offer a better understanding of the effect of the transition metals’ small metal cluster and their coordination and stabilization within g-C 3 N 4 , contributing to the rational hybrid catalyst design with a less-toxic impact on the environment and health. Bare g-C 3 N 4 is shown as a good support candidate for atom-economy-designed catalysts for hydrogenation application. In addition, cytotoxicity to the keratinocyte human HaCaT cell line revealed that low concentrations of catalysts particles (to 6.25 μg mL –1 ) did not cause degenerative changes.

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Section: Resultssupporting

confidence: 67%

Section: Resultsmentioning

confidence: 99%

Developing Benign Ni/g-C₃N₄ Catalysts for CO₂ Hydrogenation: Activity and Toxicity Study

Pieta

Gieroba

Kalisz

et al. 2022

Ind. Eng. Chem. Res.

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“…Recently, g-C 3 N 4 with 2D conjugated planes with repeated tri-s-triazine units through an interlayer has received more and more attention due to the high visible light response and stability. 109,131,[222][223][224][225] More specically, the unique tri-s-triazine structure induced N/C-coordinating framework in g-C 3 N 4 promoted the intercalation or binding of atoms into g-C 3 N 4 , which can be used as a substrate for anchoring metal SAs as a high-performance photocatalyst for the HER. Isolated and highly dispersed Pt SAs were anchored on g-C 3 N 4 (Pt SAs/g-C 3 N 4 ) to obtain high Pt atom utilization efficiency and to boost the photocatalytic performance for the HER.…”

Section: Detection and Characterization Of Sacsmentioning

confidence: 99%

Single-atom catalysts for high-efficiency photocatalytic and photoelectrochemical water splitting: distinctive roles, unique fabrication methods and specific design strategies

Liu

Ran

et al. 2022

J. Mater. Chem. A

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“…A number of atomically dispersed single-atom catalysts based on both noble metals (i.e., Au, Pt, Pd, Ru, Ir) [39,[76][77][78][79][80] and nonnoble metals (i.e., Fe, Co, Ni, Mn, Co, Mo, W) [37,41,[81][82][83][84][85] have been successfully synthesized over the last decade by utilizing various high-surface-area support materials, such as nanostructured carbons, metal oxides/carbides/nitrides/sulfides, and 2D nanostructures. To synthesize SACs with high metal-loading and durability features, the selection of support materials with well-defined anchoring sites is crucial.…”

Section: Enhancing Metal-support Interactions Via Surface Modificatio...mentioning

confidence: 99%

Modulating the Local Coordination Environment of Single‐Atom Catalysts for Enhanced Catalytic Performance in Hydrogen/Oxygen Evolution Reaction

Tomboc

Kim

Jung

et al. 2022

Small

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source could provide an auspicious alternative for reducing humanity's dependency on fossil fuels, thus lowering their environmental impact. [1][2][3][4][5] Electrochemical water splitting technology is intended for the large-scale production of high-purity H 2 . The primary reaction in the electrochemical water splitting cell is divided into two half-reactions: the oxygen evolution reaction (OER), which takes place in the anode, and the hydrogen evolution reaction (HER), which takes place in the cathode. The overall chemical reaction is simplified as H 2 O → H 2 (cathode) + ½ O 2 (anode), which can theoretically proceed with a minimum energy input of ΔG = 237.1 kJ mol −1 at a thermodynamic potential of 1.23 V. Nevertheless, the large overpotentials required to overcome the high activation barriers of the OER severely hinder the mass production of H 2 via electrochemical water splitting. [2,[6][7][8][9][10] In this regard, noble metalbased catalysts, such as IrO 2 /RuO 2 and Pt/C, possess great catalytic performances towards OER and HER, respectively. [11,12] The high costs and limited resources of noble metals have mandated researchers to seek alternatives in various affordable, non-noble metal-based electrocatalysts, like transition metal oxides (hydroxides), sulfides, phosphides, nitrides and carbides, and functional metal-free carbon composites. [13][14][15][16][17][18][19][20][21][22] However, these alternatives offer acceptable OER and HER catalytic performances when used in alkaline and acidic solutions, respectively, thereby limiting their practical applications. Besides, these materials are susceptible to rapid particle agglomeration during electrochemical operation, leading to limited atomic utilization efficiency. Noble metals like Pt, Pd, Ir, Rh, and Ru are still considered benchmark electrocatalytic materials for both HER and OER; hence, the development of cost-effective noble metal-based electrocatalysts is highly demanded.Previous studies pointed out that the catalytic activity of HER and OER catalysts is highly dependent on the density and chemical nature of the active sites, which can be improved via downscaling of the particle size. Single-atom catalysts (SACs) are the smallest possible size for a catalyst and could expose a larger surface area and tailor the atomic configuration and electronic structure, leading to optimal HER and OER activities. Thus, the development of SACs has become at the forefront of both Single-atom catalysts (SACs) hold the promise of utilizing 100% of the participating atoms in a reaction as active catalytic sites, achieving a remarkable boost in catalytic efficiency. Thus, they present great potential for noble metal-based electrochemical application systems, such as water electrolyzers and fuel cells. However, their practical applications are severely hindered by intrinsic complications, namely atom agglomeration and relocation, originating from the uncontrollably high surface energy of isolated singleatoms (SAs) during postsynthetic treatment processes or catalytic ...

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DFT calculations for single-atom confinement effects of noble metals on monolayer g-C₃N₄ for photocatalytic applications

Abstract: Graphitic carbon nitride, as a very promising two-dimensional structure host for single atom catalysts (SACs), has been studied extensively due to its significant confinement effects of single atoms for photocatalytic applications.

Cited by 41 publications

References 69 publications

Developing Benign Ni/g-C₃N₄ Catalysts for CO₂ Hydrogenation: Activity and Toxicity Study

Developing Benign Ni/g-C₃N₄ Catalysts for CO₂ Hydrogenation: Activity and Toxicity Study

Single-atom catalysts for high-efficiency photocatalytic and photoelectrochemical water splitting: distinctive roles, unique fabrication methods and specific design strategies

Modulating the Local Coordination Environment of Single‐Atom Catalysts for Enhanced Catalytic Performance in Hydrogen/Oxygen Evolution Reaction

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DFT calculations for single-atom confinement effects of noble metals on monolayer g-C3N4 for photocatalytic applications

Abstract: Graphitic carbon nitride, as a very promising two-dimensional structure host for single atom catalysts (SACs), has been studied extensively due to its significant confinement effects of single atoms for photocatalytic applications.

Cited by 41 publications

References 69 publications

Developing Benign Ni/g-C3N4 Catalysts for CO2 Hydrogenation: Activity and Toxicity Study

Developing Benign Ni/g-C3N4 Catalysts for CO2 Hydrogenation: Activity and Toxicity Study

Single-atom catalysts for high-efficiency photocatalytic and photoelectrochemical water splitting: distinctive roles, unique fabrication methods and specific design strategies

Modulating the Local Coordination Environment of Single‐Atom Catalysts for Enhanced Catalytic Performance in Hydrogen/Oxygen Evolution Reaction

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DFT calculations for single-atom confinement effects of noble metals on monolayer g-C₃N₄ for photocatalytic applications

Developing Benign Ni/g-C₃N₄ Catalysts for CO₂ Hydrogenation: Activity and Toxicity Study

Developing Benign Ni/g-C₃N₄ Catalysts for CO₂ Hydrogenation: Activity and Toxicity Study