Singlet Oxygen-Engaged Selective Photo-Oxidation over Pt Nanocrystals/Porphyrinic MOF: The Roles of Photothermal Effect and Pt Electronic State

Abstract

The selectivity control toward aldehyde in the aromatic alcohol oxidation remains a grand challenge using molecular oxygen under mild conditions. In this work, we designed and synthesized Pt/PCN-224(M) composites by integration of Pt nanocrystals and porphyrinic metal-organic frameworks (MOFs), PCN-224(M). The composites exhibit excellent catalytic performance in the photo-oxidation of aromatic alcohols by 1 atm O at ambient temperature, based on a synergetic photothermal effect and singlet oxygen production. Additionally, in opposition to the function of the Schottky junction, injection of hot electrons from plasmonic Pt into PCN-224(M) would lower the electron density of the Pt surface, which thus is tailorable for the optimized catalytic performance via the competition between the Schottky junction and the plasmonic effect by altering the light intensity. To the best of our knowledge, this is not only an unprecedented report on singlet oxygen-engaged selective oxidation of aromatic alcohols to aldehydes but also the first report on photothermal effect of MOFs.

Ultrathin 2D Zirconium Metal–Organic Framework Nanosheets: Preparation and Application in Photocatalysis

“…As we know, porphyrin compounds are extensively used for 1 O 2 generation in photocatalysis due to their high efficiency in light harvesting . A series of photochemical experiments was conducted.…”

“…Moreover, 2,2,6,6‐tetramethyl‐4‐piperidone hydrochloride (4‐oxo‐TMP) was able to trap 1 O 2 to afford the stable nitroxide radical 4‐oxo‐TEMPO, which could be measured through electron spin resonance (ESR). To our delight, a triplet with a g value of 2.006 assigned to the characteristic signal of 4‐oxo‐TEMPO for UNs‐FA was successfully detected, which further confirmed the 1 O 2 generation (Figure c) . As a proof‐of‐concept application, the UNs‐FA was used as catalyst for the photooxidation of 1,5‐dihydroxynaphthalene (1,5‐DHN) to synthesize juglone.…”

Surface Plasmon Resonance‐Enhanced Visible‐NIR‐Driven Photocatalytic and Photothermal Catalytic Performance by Ag/Mesoporous Black TiO2 Nanotube Heterojunctions

“…[13][14][15][16] Meanwhile, photothermal catalysis has attracted more and more attention. [17][18][19][20] Ap ossible approachf or efficient conversion of solar energy is based on the photothermal effect of nanoparticles (NPs) to generate hot carrierst op articipate in redox reactions, or to dissipate the absorbed photon energy into heat to accelerate the reactionrate. [21][22][23][24][25] Titanium dioxide (TiO 2 )i st he most representative material for photocatalysis, which has the advantages of low cost, nontoxic, high photoelectric conversione fficiency,h igh photocata-lytic activity,h igh chemicals tability,l arge specific surface area and pore volume.…”

Effective Singlet Oxygen Generation in Silica‐Coated CsPbBr3 Quantum Dots through Energy Transfer for Photocatalysis

“…As a kind of active oxygen, singlet oxygen has broad prospects in various applications such as selective organic synthesis, photodynamic therapy,and wastewater treatment because of its high oxidizability and reactivity. [29][30][31][32] The photosensitizer is an ecessary condition for generating singlet oxygen because the triplet molecular oxygen ( 3 O 2 )c annotb ed irectly excited to become 1 O 2 . [33] When the photosensitizer is in the lowest excited singlet state (S1), it absorbs light and then convertst ot he lowest excited triplet state (T1), and then transfers the energy to 3 O 2 to generate 1 O 2 .…”