Accelerated Photolysis of H<sub>2</sub>O<sub>2</sub> at the Air–Water Interface of a Microdroplet

Rao, Zepeng; Fang, Ye-Guang; Pan, Yishuai; Yu, Wanchao; Chen, Baoliang; Francisco, Joseph S.; Zhu, Chongqin; Chu, Chiheng

doi:10.1021/jacs.3c08101

Cited by 6 publications

(3 citation statements)

References 57 publications

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“…Molecules located at the water–air interface of aqueous aerosol droplets may show photochemistry that is modified from that in the gas phase, as exemplified by calculations from Francisco and co-workers for hydrogen peroxide (H 2 O 2 ) on a water droplet surface . Because the H 2 O 2 adopts a different geometry at the interface than in the bulk solution or the gas phase, its UV absorption band shifts to longer wavelength and better overlaps the solar spectrum, which accelerates its photolysis by tropospheric solar radiation to produce OH radicals.…”

Section: Theoretical and Computational Atmospheric Photochemistrymentioning

confidence: 99%

Perspective on Theoretical and Experimental Advances in Atmospheric Photochemistry

Curchod,

Orr-Ewing

2024

J. Phys. Chem. A

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Research that explores the chemistry of Earth's atmosphere is central to the current understanding of global challenges such as climate change, stratospheric ozone depletion, and poor air quality in urban areas. This research is a synergistic combination of three established domains: earth observation, for example, using satellites, and in situ field measurements; computer modeling of the atmosphere and its chemistry; and laboratory measurements of the properties and reactivity of gas-phase molecules and aerosol particles. The complexity of the interconnected chemical and photochemical reactions which determine the composition of the atmosphere challenges the capacity of laboratory studies to provide the spectroscopic, photochemical, and kinetic data required for computer models. Here, we consider whether predictions from computational chemistry using modern electronic structure theory and nonadiabatic dynamics simulations are becoming sufficiently accurate to supplement quantitative laboratory data for wavelength-dependent absorption cross-sections, photochemical quantum yields, and reaction rate coefficients. Drawing on presentations and discussions from the CECAM workshop on Theoretical and Experimental Advances in Atmospheric Photochemistry held in March 2024, we describe key concepts in the theory of photochemistry, survey the state-of-the-art in computational photochemistry methods, and compare their capabilities with modern experimental laboratory techniques. From such considerations, we offer a perspective on the scope of computational (photo)chemistry methods based on rigorous electronic structure theory to become a fourth core domain of research in atmospheric chemistry.

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Section: Theoretical and Computational Atmospheric Photochemistrymentioning

confidence: 99%

Perspective on Theoretical and Experimental Advances in Atmospheric Photochemistry

Curchod,

Orr-Ewing

2024

J. Phys. Chem. A

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“…Few studies have comprehensively addressed the impacts of these reaction environments on surface radicals and their conversion. Notably, various liquid/solid interfacial environments including microdroplets, , poor wettable surface, and hydrophobic surfaces , have demonstrated significant influences on the formation of H 2 O 2 . Therefore, a rigorous examination of the impact of reaction environment on the mechanism and kinetics of H 2 O 2 and O 2 evolution is imperative.…”

Section: Introductionmentioning

confidence: 99%

Weakened Interfacial Hydrogen Bond Connectivity Drives Selective Photocatalytic Water Oxidation toward H₂O₂ at Water/Brookite-TiO₂ Interface

Ren,

Zhou,

Wang

2024

J. Am. Chem. Soc.

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The formation of H 2 O 2 through the two-electron photocatalytic water oxidation reaction (WOR) is significant but encounters the competition with the four-electron O 2 evolution reaction. Recent studies showed a crystal-phase dependence in H 2 O 2 selectivity, where high purity brookite TiO 2 (b-TiO 2 ) exhibits remarkable H 2 O 2 selectivity in contrast to the common rutile phase TiO 2 (r-TiO 2 ). However, the origin of such a structure-induced selectivity preference remains elusive, primarily due to the complexities associated with the solid−liquid interface system and excited-state chemistry. Herein, we conducted a comprehensive investigation into the selectivity mechanism of WOR at the water/b-TiO 2 (210) and water/r-TiO 2 (110) interfaces, employing first-principles molecular dynamics simulations and microkinetic analyses. Intriguingly, our results reveal that the intrinsic catalytic ability of the b-TiO 2 (210) itself does not enhance H 2 O 2 selectivity compared to r-TiO 2 (110). Instead, it is the weakened interfacial hydrogen bond connectivity, modulated by the herringbone-like local atomic structure of the b-TiO 2 (210) surface, that determines the selectivity. Specifically, this weakened H-bond connectivity (i.e., local low water density) at the interface, owing to the strong water adsorption and distinct adsorption orientation, can stabilize the OH • radical and inhibit its deprotonation, leading to an improved H 2 O 2 selectivity. By contrast, the relatively strong interface H-bond connectivity established over r-TiO 2 (110) accelerates the deprotonation of OH • , with the OH • coverage being 3 orders of magnitude lower than at the water/b-TiO 2 (210) interface. This study quantitatively demonstrates that the local H-bond structure (water density) at the liquid/solid interface significantly influences photocatalytic selectivity, and this insight may offer a rational approach to enhance the H 2 O 2 selectivity.

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“…Some studies claimed that liquid surfaces, especially water surfaces, may be able to accelerate chemical reactions . For example, Rao et al found that the photolysis rate of H 2 O 2 at the air–water interface of the droplets was greatly accelerated, being 1.9 × 10 3 times faster than that in the aqueous phase. Kusaka et al used ultrafast phase-sensitive interface-selective nonlinear vibration spectroscopy to detect the photochemical reaction at the air–water interface.…”

Section: Introductionmentioning

confidence: 99%

Study on the Transport Properties of SO₂ and NO at the Interface of H₂O₂ Solutions Using Molecular Dynamics

Lin,

Tian,

Huang

et al. 2024

J. Phys. Chem. B

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Gas−liquid interfaces have a unique structure different from the bulk phase due to the complex intermolecular interactions within them and are regarded as barriers that prevent gases from entering solution or as channels that affect gas reactions. In this study, the adsorption and mass-transfer mechanisms of sulfur dioxide and nitric oxide at the gas−liquid interface of a H 2 O 2 solution were comprehensively analyzed using molecular dynamics (MD) simulations. The analysis on molecule angle showed that H 2 O molecules tended to align parallel to the solution surface on the surface of the H 2 O 2 solution. Regardless of whether the gas was adsorbed on the surface of the solution or not, H 2 O 2 molecules were always perpendicular to the interface of the solution. The analysis on molecule angle and radial distribution function revealed that the H atoms of H 2 O molecules had a corresponding turn, and SO 2 molecules were greatly affected by the attraction of H 2 O 2 molecules during the adsorption of gas molecules on the interface. Steered MD was utilized to investigate the mass-transfer process of SO 2 and NO molecules across the gas−liquid interface. The S atoms of SO 2 molecules were significantly influenced by H 2 O 2 molecules, while the O atoms of NO molecules gradually transitioned from the gas phase to the liquid phase. The results provided information on how gas molecules interacted with the surface of the solution and the specific details of the molecular orientation at the solution surface.

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Accelerated Photolysis of H₂O₂ at the Air–Water Interface of a Microdroplet

Cited by 6 publications

References 57 publications

Perspective on Theoretical and Experimental Advances in Atmospheric Photochemistry

Perspective on Theoretical and Experimental Advances in Atmospheric Photochemistry

Weakened Interfacial Hydrogen Bond Connectivity Drives Selective Photocatalytic Water Oxidation toward H₂O₂ at Water/Brookite-TiO₂ Interface

Study on the Transport Properties of SO₂ and NO at the Interface of H₂O₂ Solutions Using Molecular Dynamics

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Accelerated Photolysis of H2O2 at the Air–Water Interface of a Microdroplet

Cited by 6 publications

References 57 publications

Perspective on Theoretical and Experimental Advances in Atmospheric Photochemistry

Perspective on Theoretical and Experimental Advances in Atmospheric Photochemistry

Weakened Interfacial Hydrogen Bond Connectivity Drives Selective Photocatalytic Water Oxidation toward H2O2 at Water/Brookite-TiO2 Interface

Study on the Transport Properties of SO2 and NO at the Interface of H2O2 Solutions Using Molecular Dynamics

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About

Accelerated Photolysis of H₂O₂ at the Air–Water Interface of a Microdroplet

Weakened Interfacial Hydrogen Bond Connectivity Drives Selective Photocatalytic Water Oxidation toward H₂O₂ at Water/Brookite-TiO₂ Interface

Study on the Transport Properties of SO₂ and NO at the Interface of H₂O₂ Solutions Using Molecular Dynamics