Multiphase Electrochemiluminescence of Microdroplets and Radical Salts DOI
Brady R. Layman,

Daniel M. Carrel,

Jeffrey E. Dick

и другие.

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Июнь 3, 2025

ConspectusOver the past decade, experiments involving microdroplets have challenged framework of chemistry. These droplets constitute a multiphase system, where dynamic interplay between solid, liquid, and gas influences reactions. Multiphase systems are prevalent in nature possess unique physicochemical properties. However, chemistry, phase boundary reactivity is often overlooked because molecules experience "bulk" reactivity. biological processes, such as cell mitosis, sensor technology, organic synthesis, pollution remediation.Recently, our group has developed different strategies electrochemiluminescence (also called electrogenerated chemiluminescence, both shortened to ECL) microscopy imaging understand properties dynamics at electrified interfaces. ECL takes advantage luminophore that radically annihilates with strong oxidizing or reducing reagent. If enthalpy annihilation high enough, will be left an excited state radiatively decay, producing light. Thus, requires no incident light, analytical figures merit due light being emitted close interface (1-10 μm), providing insight into within electrode's proximity.This Account detail group's efforts discovering reactions environments exhibiting native triphasic (liquid|liquid|electrode) interfaces new phases formed (e.g., bubble nucleation electroprecipitation). We first began developing tools necessary image liquid|liquid discovered that, when neighboring fuse together, small pockets (inclusions) continuous existed inside merged droplets. Studies inclusion chemical led interesting observation on can act micropumps, protecting electrode from buildup during electrocatalytic reactions.Even though strength emission confined directly surface, this also significant weakness, considering phenomena occur far away surface. One recent thrust community ways using phenomenon termed "Through-Space ECL". Our used technique measure forces boundaries surface.By playing relative solubilities reactants products, we showed if radical ion generated precipitates more quickly than its lifetime, salts formed. way fossilize highly energetic molecules. seemingly tenet effectively bottle up ECL, fossilizing elsewhere space time. Given passion teach world beauties electrochemistry, concepts surrounding pedagogically innovate performed by children visualize competing reactions.In depict current spectroscopy focus contributions burgeoning field. field been discuss probability impact across sciences moving forward.

Язык: Английский

Methane Bubbled Through Seawater Can be Converted to Methanol With High Efficiency DOI Creative Commons
Xiaowei Song, Chanbasha Basheer, Jinheng Xu

и другие.

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 21, 2025

Partial oxidation of methane (POM) is achieved by forming air-methane microbubbles in saltwater to which an alternating electric field applied using a copper oxide foam electrode. The solubility increased putting it contact with water containing dissolved KCl or NaCl (3%). Being fully dispersed as (20-40 µm diameter), reacts more hydroxyl radicals (OH·) at the gas-water interface. voltage (100 mV) generates two synergistic POM processes dominated Cl- → Cl· + e- and O2 -• under positive negative potentials, respectively. By tuning frequency amplitude, extent path process can be precisely controlled so that than 90% methanol selectively formed compared byproducts, dichloromethane, acetic acid. conversion yield estimated 57% rate approximately 887 µM h-1. This method appears have potential for removing from air seawater converting higher-concentration sources into value-added methanol.

Язык: Английский

Процитировано

1
Inverted Microdroplets (Microbubbles) Induced Interfacial Water Protonation to Promote Alkaline Release of Amine and Reduce Energy in CCS DOI
Yuewei Fan, Lu Chen, Haoyu Meng

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Май 9, 2025

This study engineered a superacidic interface with pronounced polar electric field within the amine-water system by inducing hydrogen bond charge transfer in interfacial water via inverted microdroplets (microbubbles), thereby stabilizing protons layer. mechanism enabled continuous alkaline release of hindered amines (AMP-MIS), enhancing CO2 absorption load capacity and reducing regeneration energy consumption. Nuclear magnetic resonance potentiometric titration elucidated product distribution, while Raman spectroscopy, pH analysis, conductivity measurements confirmed proton stabilization. Theoretical calculations provided insights into reaction mechanism. Pilot-scale testing revealed AMP-MIS achieved 74.2% increase cyclic capacity, surpassing conventional 30 wt % MEA system, reduced from 3.667 GJ/t to 1.885 CO2. innovative strategy offers valuable guidance for advancing amine-based decarbonization technologies carbon emissions power industry, representing pivotal step toward neutrality.

Язык: Английский

Процитировано

0
Real-Time Visualization of an Elusive, Strong Reducing Agent during Tris(2,2'-bipyridyl)ruthenium(II) Electro-Oxidation in Water DOI
Megan L. Hill, Brady R. Layman, Jeffrey E. Dick

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Май 16, 2025

Recently, liquid|liquid and liquid|gas interfaces have been implicated in driving unexpected chemistries, including dramatic rate enhancement spontaneous redox reactions. Given such studies, new methods are necessary to observe implicate reactive species. Tris(2,2'-bipyridyl)ruthenium(II) ([Ru(bpy)3]2+) is a common luminophore for photoluminescence electrochemiluminescence (ECL) studies. In this work, we demonstrate that the electro-oxidation of [Ru(bpy)3]2+ water produces light without addition sacrificial coreactants. We studied by confining an aqueous droplet adhered both tin-doped indium oxide electrode and, separately, glassy carbon inlaid disc macroelectrode (d = 3 mm). also generalized method observation at larger electrodes. The intensity higher absence O2, diminishes when adding H2O2, disappears presence well-behaved, one-electron oxidant (hexaammineruthenium(III)). Our results indicate powerful reducing agent present during [Ru(bpy)3]2+. This least energetic enough create excited state, [Ru(bpy)3]2+*, giving minimum energy ∼2 eV. Chemiluminescence persists as [Ru(bpy)3]3+ diffuses into solution, indicating strong may exist natively low abundance. These observations significant fundamental ramifications because they elucidate pathway ECL allow real-time visualization highly

Язык: Английский

Процитировано

0
Multiphase Electrochemiluminescence of Microdroplets and Radical Salts DOI
Brady R. Layman,

Daniel M. Carrel,

Jeffrey E. Dick

и другие.

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Июнь 3, 2025

ConspectusOver the past decade, experiments involving microdroplets have challenged framework of chemistry. These droplets constitute a multiphase system, where dynamic interplay between solid, liquid, and gas influences reactions. Multiphase systems are prevalent in nature possess unique physicochemical properties. However, chemistry, phase boundary reactivity is often overlooked because molecules experience "bulk" reactivity. biological processes, such as cell mitosis, sensor technology, organic synthesis, pollution remediation.Recently, our group has developed different strategies electrochemiluminescence (also called electrogenerated chemiluminescence, both shortened to ECL) microscopy imaging understand properties dynamics at electrified interfaces. ECL takes advantage luminophore that radically annihilates with strong oxidizing or reducing reagent. If enthalpy annihilation high enough, will be left an excited state radiatively decay, producing light. Thus, requires no incident light, analytical figures merit due light being emitted close interface (1-10 μm), providing insight into within electrode's proximity.This Account detail group's efforts discovering reactions environments exhibiting native triphasic (liquid|liquid|electrode) interfaces new phases formed (e.g., bubble nucleation electroprecipitation). We first began developing tools necessary image liquid|liquid discovered that, when neighboring fuse together, small pockets (inclusions) continuous existed inside merged droplets. Studies inclusion chemical led interesting observation on can act micropumps, protecting electrode from buildup during electrocatalytic reactions.Even though strength emission confined directly surface, this also significant weakness, considering phenomena occur far away surface. One recent thrust community ways using phenomenon termed "Through-Space ECL". Our used technique measure forces boundaries surface.By playing relative solubilities reactants products, we showed if radical ion generated precipitates more quickly than its lifetime, salts formed. way fossilize highly energetic molecules. seemingly tenet effectively bottle up ECL, fossilizing elsewhere space time. Given passion teach world beauties electrochemistry, concepts surrounding pedagogically innovate performed by children visualize competing reactions.In depict current spectroscopy focus contributions burgeoning field. field been discuss probability impact across sciences moving forward.

Язык: Английский

Процитировано

0