Violet phosphorus quantum dots as an emerging visible light-responsive photocatalyst for an efficient hydrogen evolution reaction

Wang, Xin; Chen, Xu; Wang, Ziyou; Wang, Yan; Zhao, Xuewen; Zhang, Jinying; Ma, Ming; Guo, Quansheng; Zhang, Fuxiang

doi:10.1039/d3ta02021e

“…Hydrogen energy, as a promising alternative to fossil fuels, is clean, efficient, sustainable, “carbon‐free”, and has inspired wide interests [4–8] . The use of solar energy for photocatalytic water splitting to produce hydrogen is a promising strategy to solve the energy crisis and the development of efficient artificial photocatalysts is one of the most critical issues in this field [9–19] . However, compared with traditional thermal catalysis, the photocatalytic reaction involves multiple processes including photoexcitation and photogenerated carrier separation, which poses a greater barrier for regulating the photocatalytic performance [20] .…”

Section: Introductionmentioning

confidence: 99%

Promoted Photocatalytic Hydrogen Evolution by Tuning the Electronic State of Copper Sites in Metal‐Organic Supramolecular Assemblies

Liu,

Jiang,

Chen

et al. 2023

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The electronic state in terms of charge and spin of metal site is fundamental to govern the catalytic activity of photocatalyst. Herein, we show that the modulation of electronic states of Cu sites without changing the coordination environments of two metal‐organic supramolecular assemblies only based on π⋅⋅⋅π stacking can significantly improve the photocatalytic activity. As heterogeneous photocatalysts without using noble metal cocatalysts, the hydrogen production rate increases from 522 to 3620 μmol h−1 g−1. A systematical analysis reveals that the charge density and spin density of metal center are efficiently modulated via the modulation of coordination fields around active copper(II) centers by the variation of non‐coordination groups of terminal ligands, leading to the significant enhancement of photocatalytic activity. This work provides an insight on the electronic state of active metal center for designing high‐performance photocatalysts.

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“…Hydrogen energy, as a promising alternative to fossil fuels, is clean, efficient, sustainable, “carbon‐free”, and has inspired wide interests [4–8] . The use of solar energy for photocatalytic water splitting to produce hydrogen is a promising strategy to solve the energy crisis and the development of efficient artificial photocatalysts is one of the most critical issues in this field [9–19] . However, compared with traditional thermal catalysis, the photocatalytic reaction involves multiple processes including photoexcitation and photogenerated carrier separation, which poses a greater barrier for regulating the photocatalytic performance [20] .…”

Section: Introductionmentioning

confidence: 99%

“…[4][5][6][7][8] The use of solar energy for photocatalytic water splitting to produce hydrogen is a promising strategy to solve the energy crisis and the development of efficient artificial photocatalysts is one of the most critical issues in this field. [9][10][11][12][13][14][15][16][17][18][19] However, compared with traditional thermal catalysis, the photocatalytic reaction involves multiple processes including photoexcitation and photogenerated carrier separation, which poses a greater barrier for regulating the photocatalytic performance. [20] In general, the microenvironment of catalytic sites governs the electronic structures and hence determine the photocatalytic performance, but the roles at atomic levels are still far from being controlled.…”

Section: Introductionmentioning

confidence: 99%

Promoted Photocatalytic Hydrogen Evolution by Tuning the Electronic State of Copper Sites in Metal‐Organic Supramolecular Assemblies

Liu,

Jiang,

Chen

et al. 2023

Angewandte Chemie

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0

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The electronic state in terms of charge and spin of metal site is fundamental to govern the catalytic activity of photocatalyst. Herein, we show that the modulation of electronic states of Cu sites without changing the coordination environments of two metal‐organic supramolecular assemblies only based on π⋅⋅⋅π stacking can significantly improve the photocatalytic activity. As heterogeneous photocatalysts without using noble metal cocatalysts, the hydrogen production rate increases from 522 to 3620 μmol h−1 g−1. A systematical analysis reveals that the charge density and spin density of metal center are efficiently modulated via the modulation of coordination fields around active copper(II) centers by the variation of non‐coordination groups of terminal ligands, leading to the significant enhancement of photocatalytic activity. This work provides an insight on the electronic state of active metal center for designing high‐performance photocatalysts.

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P‐N Bonds‐Mediated Atomic‐Level Charge‐Transfer Channel Fabricated between Violet Phosphorus and Carbon Nitride Favors Charge Separation and Water Splitting

Wang,

Ma

et al. 2024

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Heterostructures are widely employed in photocatalysis to promote charge separation and photocatalytic activity. However, their benefits are limited by the linkages and contact environment at the interface. Herein, violet phosphorus quantum dots (VPQDs) and graphitic carbon nitride (g‐C3N4) are employed as model materials to form VPQDs/g‐C3N4 heterostructures by a simple ultrasonic pulse excitation method. The heterostructure contains strong interfacial P‐N bonds that mitigate interfacial charge‐separation issues. P‐P bond breakage occurs in the distinctive cage‐like [P9] VPQD units during longitudinal disruption, thereby exposing numerous active P sites that bond with N atoms in g‐C3N4 under ultrasonic pulse excitation. The atomic‐level interfacial P–N bonds of the Z‐scheme VPQDs/g‐C3N4 heterostructure serve as photogenerated charge‐transfer channels for improved electron‐hole separation efficiency. This results in excellent photocatalytic performance with a hydrogen evolution rate of 7.70 mmol g−1 h−1 (over 9.2 and 8.5 times greater than those of pure g‐C3N4 and VPQDs, respectively) and apparent quantum yield of 11.68% at 400 nm. Using atomic‐level chemical bonds to promote interfacial charge separation in phosphorene heterostructures is a feasible and effective design strategy for photocatalytic water‐splitting materials.

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Violet phosphorus quantum dots as an emerging visible light-responsive photocatalyst for an efficient hydrogen evolution reaction

Abstract: The development of visible light-responsive semiconductor photocatalysts has inspired extensive interest, but its number is very limited for the quantum dots (QDs)-based ones. Herein, an emerging mono-elemental material, violet phosphorus...

Cited by 11 publications

References 59 publications

Promoted Photocatalytic Hydrogen Evolution by Tuning the Electronic State of Copper Sites in Metal‐Organic Supramolecular Assemblies

Promoted Photocatalytic Hydrogen Evolution by Tuning the Electronic State of Copper Sites in Metal‐Organic Supramolecular Assemblies

Promoted Photocatalytic Hydrogen Evolution by Tuning the Electronic State of Copper Sites in Metal‐Organic Supramolecular Assemblies

P‐N Bonds‐Mediated Atomic‐Level Charge‐Transfer Channel Fabricated between Violet Phosphorus and Carbon Nitride Favors Charge Separation and Water Splitting

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