Efficient reduction of highly toxic 4-nitrophenol with ultra-low platinum loading on cobalt (II, III) oxide support: Facile synthesis and high turnover frequency

International Journal of Hydrogen Energy, Journal Year: 2025, Volume and Issue: 102, P. 800 - 815

Published: Jan. 11, 2025

Language: Английский

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Functional Analytic Derivation and CP2K Implementation of the SCCS Model Based on the Solvent-Aware Interface

Computer Physics Communications, Journal Year: 2025, Volume and Issue: unknown, P. 109563 - 109563

Published: Feb. 1, 2025

Language: Английский

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Competing Nonadiabatic Relaxation Pathways for Near-UV Excited ortho-Nitrophenol in Aqueous Solution

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(36), P. 9153 - 9159

Published: Aug. 29, 2024

Nitrophenols are atmospheric pollutants found in brown carbon aerosols produced by biomass burning. Absorption of solar radiation these nitrophenols contributes to radiative forcing, but quantifying this climate impact requires better understanding their photochemical pathways. Here, the photochemistry near-UV (λ = 350 nm) excited ortho-nitrophenol aqueous solution is investigated using transient absorption spectroscopy and time-resolved infrared over fs μs time scale characterize states, intermediates, photoproducts. Interpretation data supported quantum chemical calculations linear-response time-dependent density functional theory (LR-TDDFT). Our results indicate efficient nonradiative decay via an S1(ππ*)/S0 conical intersection leading hot ground state which vibrationally cools solution. A previously unreported minor pathway involves intersystem crossing near S1(nπ*) minimum, with resulting triplet facilitated deprotonation. These relaxation pathways account for low yields photodegradation.

Language: Английский

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Excited-State Decay and Photolysis of O-Nitrophenol after Proton Transfer. II: A Theoretical Investigation in the Microsolvated Atmospheric Environment

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(43), P. 9486 - 9496

Published: Oct. 17, 2024

Changes in atmospheric humidity affect the number of water molecules surrounding o-nitrophenol (ONP), creating an anisotropic chemical environment. It, turn, influences photodynamic behaviors ONP, differing from those observed gas phase and solution. Recently, we explored excited-state decay generation hydroxyl (OH) radical before proton transfer ONP microsolvated environment using MS-CASPT2//CASSCF approach. As is well known, capable converting to its aci-nitro isomer (aciONP) via intramolecular (ESIPT) process. In present work, photoinduced dynamics aciONP, which can lead OH nitrous acid (HONO), was studied same computational model. Our calculations demonstrated that increasing affects molecular geometries, particularly key bond lengths dihedral angles HONO group, while also reducing relative energies minima intersections. Moreover, identified two distinct types minimum structures: one retains hydrogen other breaks with H atom flipping outward. The latter structure, compared former, has a different electronic-state character facilitates intersystem crossing processes. Subsequently, major paths were proposed: (PATH I) ESIPT → S1 S1S0 S0; II) S1-2 S1T1 T1 S0T1 S0. Furthermore, state relatively long lifetime, allowing for formation HONO, corresponding energy barriers decrease as increases. These theoretical findings provide valuable insights into photodynamics aciONP

Language: Английский

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Excited-State Decay and Photolysis of O-Nitrophenol before Proton Transfer. I: A Theoretical Investigation in the Microsolvated Atmospheric Environment

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(43), P. 9497 - 9509

Published: Oct. 19, 2024

As a potential source of the hydroxyl (OH) radical and nitrous acid (HONO), photolysis

Language: Английский

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