Photo-generated reactive oxygen species assisted tandem amine homocoupling and amine-alcohol cross-coupling reaction on mesoporous spinel cobalt oxide

Kapuge, Tharindu Kankanam; Thalgaspitiya, Wimalika R.K.; Rathnayake, Dinithi; He, Junkai; Kerns, Peter; Suib, Steven L.

doi:10.1016/j.apcatb.2019.118386

Title: Photo-generated reactive oxygen species assisted tandem amine homocoupling and amine-alcohol cross-coupling reaction on mesoporous spinel cobalt oxide

Journal Article · Tue Nov 05 00:00:00 EST 2019 · Applied Catalysis B: Environmental

DOI:https://doi.org/10.1016/j.apcatb.2019.118386· OSTI ID:1800624

Kapuge, Tharindu Kankanam ^[1]; Thalgaspitiya, Wimalika R.K. ^[1]; Rathnayake, Dinithi ^[1]; He, Junkai ^[1]; Kerns, Peter ^[1];

^[1]

Univ. of Connecticut, Storrs, CT (United States)

Mesoporous spinel cobalt oxide (Co₃O₄) with fine-tuned pore size distributions (9.6–17.6 nm) and different surface areas (33–85 m²/g) were synthesized using a series of nonionic surfactants. A direct influence of the chemical composition of the surfactants and calcination temperature on crystallite size, morphology, pore size/volume, surface area, valance band edge, and Co²⁺/Co³⁺ ratio was recognized. Correlation between the aforementioned factors, transition metal ion incorporation and benzylamine homocoupling reaction was discussed. Shape-specific binding of amine on the cobalt oxide active sites was proposed based on substrate scope study. Tandem synthesis strategy to selectively synthesize amine (aliphatic/aromatic) homo-coupled imines and amine-alcohol cross-coupled imines was introduced. Low-intensity light-induced singlet oxygen and hydroxyl radical-mediated reaction mechanism was proposed based on the EPR, XPS, photoreactor, and reactive oxygen species scavenger tests. Selective and switchable synthesis of homo-coupled (yield 85%) and cross-coupled (yield 87%) products was achieved with sodium azide and mannitol additives.

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Research Organization:: Univ. of Connecticut, Storrs, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-86ER13622

OSTI ID:: 1800624

Alternate ID(s):: OSTI ID: 1602891

Journal Information:: Applied Catalysis B: Environmental, Vol. 268; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 13 works

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54 ENVIRONMENTAL SCIENCES
mesoporous
cobalt oxide
surfactant
singlet oxygen
hydroxyl radical
benzylamine
alcohol
photocatalyst

Title: Photo-generated reactive oxygen species assisted tandem amine homocoupling and amine-alcohol cross-coupling reaction on mesoporous spinel cobalt oxide

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