4-Nitrophenylacetylene-modified Cu<sub>2</sub>O cubes and rhombic dodecahedra showing superior photocatalytic activity through surface band structure modulation

Chan, Shang-Ju; Kao, Jui‐Cheng; Chou, Po-Jung; Lo, Yu‐Chieh; Chou, Jyh‐Pin; Huang, Michael H.

doi:10.1039/d2tc00294a

Cited by 13 publications

(40 citation statements)

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“…4 The Cu 2 O crystals were then mixed with K 2 CO 3 and 4-nitrophenylacetylene for 12 h at room temperature to functionalize the crystals. 14 XRD patterns of the synthesized Cu 2 O cubes and rhombic dodecahedra and after 4-NA functionalization are shown in Figure S2. Although the XRD peak positions before and after 4-NA modification are practically not changed, there are notable peak shifts between cubes and rhombic dodecahedra.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…4-NA modification proceeds through a Sonogashira coupling mechanism. 14 First, 4-NA forms a π-alkyne complex with the Cu(I) cation, which enhances the acidity of the alkyne proton. 33 The carbonate anion then removes the acidic terminal proton to generate a highly reactive acetylide anion, which directly reacts with a surface Cu(I) atom to give the copper acetylide complex.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The weak signal at ν̃= 2109 cm −1 is the signal of C�C triple bond stretching. 35 Furthermore, the peaks of other functional groups, such as the C�C double bond in the benzene ring and N−O stretching and C−N stretching in the nitro group, could be found at ν̃= 1591 cm −1 , 1506 cm −1 , and 14 The large surface electron density change from molecular functionalization can weaken some infrared bands. This is also the reason why inert Cu 2 O cubes become highly photocatalytically active after 4-NA modification.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…K 2 CO 3 (14.7 mg, 0.105 mmol), 4-nitrophenylacetylene (15.4 mg, 0.105 mmol), and Cu 2 O crystals (10 mg) were added to a 4 mL vial with a stir bar. 14 Absolute ethanol (1 mL) was then added to the vial, and the mixture was sonicated for 10 min until Cu 2 O crystals were completely dispersed and K 2 CO 3 completely dissolved in the solution. The vial was sealed and stirred for 12 h at room temperature.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…12−14 So far, 4-NA-modified Cu 2 O cubes and rhombic dodecahedra show the best photocatalytic performance. 14 Other than photodegradation of dye molecules, the photogenerated charge carriers and radicals may be utilized to catalyze organic transformations. 15 In particular, aryl sulfide oxidation can be accomplished through reaction with superoxide radicals.…”

Section: ■ Introductionmentioning

confidence: 99%

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Photocatalytic Aryl Sulfide Oxidation Using 4-Nitrophenylacetylene-Modified Cu₂O Crystals

Hsieh

et al. 2023

ACS Appl. Mater. Interfaces

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4-Nitrophenylacetylene-functionalized Cu 2 O rhombic dodecahedra and cubes have been used to photocatalyze aryl sulfide oxidation generating aryl sulfoxides. With an oxygen supply and light from a blue light-emitting diode (LED), the reaction can be completed in 12 h with a water and methanol mixed solution. Generally high product yields and excellent product selectivity of sulfoxides over sulfones were achieved. In particular, a thioanisole to methyl phenyl sulfoxide yield of 98% was obtained. A mechanistic study has revealed that photogenerated electrons, holes, and superoxide radicals are involved in the oxidation reaction. The benefit of simple photocatalyst preparation and molecular functionalization to boost catalytic performance shows that surface-controlled ionic solids can be very effective photocatalysts for some organic transformations.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Photocatalytic Aryl Sulfide Oxidation Using 4-Nitrophenylacetylene-Modified Cu₂O Crystals

Hsieh

et al. 2023

ACS Appl. Mater. Interfaces

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Experimental Revelation of Surface and Bulk Lattices in Faceted Cu₂O Crystals

Chen

Kumar

Wei

et al. 2023

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Semiconductor crystals have generally shown facet‐dependent electrical, photocatalytic, and optical properties. These phenomena have been proposed to result from the presence of a surface layer with bond‐level deviations. To provide experimental evidence of this structural feature, synchrotron X‐ray sources are used to obtain X‐ray diffraction (XRD) patterns of polyhedral cuprous oxide crystals. Cu2O rhombic dodecahedra display two distinct cell constants from peak splitting. Peak disappearance during slow Cu2O reduction to Cu with ammonia borane differentiates bulk and surface layer lattices. Cubes and octahedra also show two peak components, while diffraction peaks of cuboctahedra are comprised of three components. Temperature‐varying lattice changes in the bulk and surface regions also show shape dependence. From transmission electron microscopy (TEM) images, slight plane spacing deviations in surface and inner crystal regions are measured. Image processing provides visualization of the surface layer with depths of about 1.5–4 nm giving dashed lattice points instead of dots from atomic position deviations. Close TEM examination reveals considerable variation in lattice spot size and shape for different particle morphologies, explaining why facet‐dependent properties are emerged. Raman spectrum reflects the large bulk and surface lattice difference in rhombic dodecahedra. Surface lattice difference can change the particle bandgap.

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Density‐Functional Theory Studies on Photocatalysis and Photoelectrocatalysis: Challenges and Opportunities

Lin,

Rohilla,

Kuo

et al. 2024

Solar RRL

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Density‐functional theory (DFT) is pivotal in the advancement of photocatalysis and photoelectrocatalysis. Its capability to explore electronic structures of materials contributes significantly to clarifying the mechanisms of photocatalytic (PC) and photoelectrocatalytic (PEC) processes. DFT calculations enable a deeper understanding of how these processes work at a molecular level, which is essential for designing versatile photocatalysts and photoelectrodes and optimizing reaction pathways. In this perspective, key PC and PEC applications, such as H2 production, CO2 reduction, dye degradation, and N2 reduction, where DFT is instrumental in optimizing materials designs and reaction pathways, are highlighted. Exploration on the synergy between experimental research and DFT calculations is highlighted, which is crucial for the development of efficient and environmentally friendly energy solutions. The discussion further extends to challenges and future directions, emphasizing the need for incorporating factors, including discrepancy in scale, light illumination, electrolyte presence, and applied bias, into DFT calculations, to achieve a more comprehensive understanding of PC and PEC systems. In this perspective, it is aimed to provide a holistic view of the current state and potential advancements in photocatalyst and photoelectrode modeling, thereby guiding future research toward more effective and sustainable energy and chemical production processes in PC and PEC systems.

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4-Nitrophenylacetylene-modified Cu₂O cubes and rhombic dodecahedra showing superior photocatalytic activity through surface band structure modulation

Abstract: The inert Cu2O cubes exhibit a superior photocatalytic activity after functionalized with 4-nitrophenylacetylene (4-NA). The 4-NA-modifed Cu2O octahedra and rhombic dodecahedra also show significant activity enhancement. Infrared and X-ray photoelectron...

Cited by 13 publications

References 49 publications

Photocatalytic Aryl Sulfide Oxidation Using 4-Nitrophenylacetylene-Modified Cu₂O Crystals

Photocatalytic Aryl Sulfide Oxidation Using 4-Nitrophenylacetylene-Modified Cu₂O Crystals

Experimental Revelation of Surface and Bulk Lattices in Faceted Cu₂O Crystals

Density‐Functional Theory Studies on Photocatalysis and Photoelectrocatalysis: Challenges and Opportunities

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4-Nitrophenylacetylene-modified Cu2O cubes and rhombic dodecahedra showing superior photocatalytic activity through surface band structure modulation

Abstract: The inert Cu2O cubes exhibit a superior photocatalytic activity after functionalized with 4-nitrophenylacetylene (4-NA). The 4-NA-modifed Cu2O octahedra and rhombic dodecahedra also show significant activity enhancement. Infrared and X-ray photoelectron...

Cited by 13 publications

References 49 publications

Photocatalytic Aryl Sulfide Oxidation Using 4-Nitrophenylacetylene-Modified Cu2O Crystals

Photocatalytic Aryl Sulfide Oxidation Using 4-Nitrophenylacetylene-Modified Cu2O Crystals

Experimental Revelation of Surface and Bulk Lattices in Faceted Cu2O Crystals

Density‐Functional Theory Studies on Photocatalysis and Photoelectrocatalysis: Challenges and Opportunities

Contact Info

Product

Resources

About

4-Nitrophenylacetylene-modified Cu₂O cubes and rhombic dodecahedra showing superior photocatalytic activity through surface band structure modulation

Photocatalytic Aryl Sulfide Oxidation Using 4-Nitrophenylacetylene-Modified Cu₂O Crystals

Photocatalytic Aryl Sulfide Oxidation Using 4-Nitrophenylacetylene-Modified Cu₂O Crystals

Experimental Revelation of Surface and Bulk Lattices in Faceted Cu₂O Crystals