Sprayed Oil-Water Microdroplets as a Hydrogen Source.

Liquid water provides the largest hydrogen reservoir on the earth's surface. Direct utilization of water as a source of hydrogen atoms and molecules is fundamental to the evolution of the ecosystem and industry. However, liquid water is an unfavorable electron donor for forming these hydrogen species owing to its redox inertness. We report oil-mediated electron extraction from water microdroplets, which is easily achieved by ultrasonically spraying an oil-water emulsion. Based on charge measurement and electron paramagnetic resonance spectroscopy, contact electrification between oil and a water microdroplet is demonstrated to be the origin of electron extraction from water molecules. This contact electrification results in enhanced charge separation and subsequent mutual neutralization, which enables a ∼13-fold increase of charge carriers in comparison with an ultrapure water spray, leading to a ∼16-fold increase of spray-sourced hydrogen that can hydrogenate CO2 to selectively produce CO. These findings emphasize the potential of charge separation enabled by spraying an emulsion of liquid water and a hydrophobic liquid in driving hydrogenation reactions.

Pyrogenic Carbon Degradation by Galvanic Coupling with Sprayed Seawater Microdroplets.

Surface waves are known for their mechanical role in coastal processes that influence the weather and climate. However, their chemical impact, particularly on the transformation of pyrogenic carbon, is poorly understood. Pyrogenic carbon is generally assumed to show negligible postformational alteration of its stable carbon isotope composition. Here we present an electrochemical interaction of pyrogenic carbon with the sprayed seawater microdroplets resulting from wave breaking, driven by the galvanic coupling between the microdroplet water-carbon interfaces and the microdroplet water-vapor interfaces. This enables refractory pyrogenic carbon to rapidly degrade via the oxygenation and mineralization reaction, which makes it ∼2.6‰ enriched in 13C, far exceeding the generally assumed postformation alteration values (<0.5‰) of pyrogenic carbon. The unique chemical dynamics of seawater microdroplets provide new insights into the discrepancy in carbon isotope signatures between riverine and marine black carbon, emphasizing the potential of coastal oceans for carbon sequestration in the global carbon cycle.

Hydrocarbon Degradation by Contact with Anoxic Water Microdroplets.

Oils are hydrophobic, but their degradation is frequently found to be accelerated in the presence of water microdroplets. The direct chemical consequences of water-oil contact have long been overlooked. We show that aqueous microdroplets in emulsified water-hexadecane (C16H34) mixtures can spontaneously produce CO2, •H, H2, and short-chain hydrocarbons (mainly C1 and C2) as detected by gas chromatography, electron paramagnetic resonance spectroscopy, and mass spectrometry. This reaction results from contact electrification at the water-oil microdroplet interface, in which reactive oxygen species are produced, such as hydrated hydroxyl radicals and hydrogen peroxide. We also find that the H2 originates from the water microdroplet and not the hydrocarbon it contacts. These observations highlight the potential of interfacial contact electrification to produce new chemistry.

Accelerating Selective Oxidation of Biomass-Based Hydroxyl Compounds with Hydrogen Bond Acceptors.

Hydrogen-bonding-initiated self-association makes the valorization of biomass-based hydroxyl compounds a formidable challenge at high concentration. Apart from enhancing the dehydration reaction of hydroxyl compounds with the noncovalent medium effects, insights into how these effects can be exploited to optimize the oxidative reactivity of concentrated hydroxyl compounds remain unclear. Herein, we elucidate that deaggregation of hydroxyl groups with a catalytic number of hydrogen bond acceptors is essential in improving the reactivity of the aerobic oxidation of biomass-based neat aromatic alcohols over the vanadium-based catalyst. The neat 5-hydroxymethylfurfural (HMF) deaggregated with 25 mol % N,N-dimethylformamide (DMF) shows a >7-fold increase in reactivity to produce corresponding aldehydes with excellent selectivity, in stark contrast to the contrary deactivation of reaction in excessive DMF.

Aprotic Amine-modified Manganese Dioxide Catalysts for Selectivity-tunable Oxidation of Amines.

Organic modifiers have shown promising potential for regulating the activity and selectivity of heterogeneous catalysts via tuning their surface properties. Despite the increasing application of organic modification technique in regulating the redox-acid catalysis of metal oxides, control of the acidity of metal oxide catalysts for enhanced reaction selectivity without sacrificing their redox activity remains a substantial challenge. Herein, we show the successful control of redox-acid catalysis of metal oxides with aprotic tertiary amine modifiers. Robust modification of manganese dioxide catalysts with N,N-dialkylcyclohexylamine selectively blocks the Lewis acid sites, with their redox activity mostly unaffected. This enables efficient synthesis of imines in high to excellent selectivity via aerobic oxidation of structurally diverse aryl amines.

Catalytic Synthesis of 2,5-Furandicarboxylic Acid from Concentrated 2,5-Diformylfuran Mediated by N-hydroxyimides under Mild Conditions.

Producing polyester monomer 2,5-furandicarboxylic acid (FDCA) from biomass as an alternative to fossil-derived terephthalic acid has drawn much attention from both academy and industry. In this work, an efficient FDCA synthesis was proposed from 10.6 wt % 2,5-diformylfuran (DFF) in acetic acid using a combined catalytic system of Co/Mn acetate and N-hydroxyimides. The intermediate product of 5-formyl-2-furandicarboxylic acid (FFCA) possesses the least reactive formyl group. N-hydroxysuccinimide was found to be superior to N-hydroxyphthalimide in catalyzing the oxidation of the formyl group in FFCA intermediate, affording a near 95 % yield of FDCA under mild conditions of 100 °C. Trace maleic anhydride was detected as by-product, which mainly came from the oxidative cleavage of DFF via furfural, furoic acid and 5-acetoxyl-2(5H)-furanone as intermediates.

Switching acidity on manganese oxide catalyst with acetylacetones for selectivity-tunable amines oxidation.

The design of metal oxide catalysts predominantly focuses on the composition or geometry engineering to enable optimized reactivity on the surface. Despite the numerous reports investigating the surface chemisorption of organic molecules on metal oxides, insights into how adsorption of organic modifiers can be exploited to optimize the catalytic properties of metal oxides are lacking. Herein, we describe the use of enolic acetylacetones to modify the surface Lewis acid properties of manganese oxide catalysts. The acetylacetone modification is stable under the reaction conditions and strongly influences the redox-acid cooperative catalysis of manganese oxides. This enables a rational control of the oxidation selectivity of structurally diverse arylmethyl amines to become switchable from nitriles to imines.

Carboxylic acid-modified metal oxide catalyst for selectivity-tunable aerobic ammoxidation.

Controlling the reaction selectivity of a heterobifunctional molecule is a fundamental challenge in many catalytic processes. Recent efforts to design chemoselective catalysts have focused on modifying the surface of metal nanoparticle materials having tunable properties. However, precise control over the surface properties of base-metal oxide catalysts remains a challenge. Here, we show that green modification of the surface with carboxylates can be used to tune the ammoxidation selectivity toward the desired products during the reaction of hydroxyaldehyde on manganese oxide catalysts. These modifications improve the selectivity for hydroxynitrile from 0 to 92% under identical reaction conditions. The product distribution of dinitrile and hydroxynitrile can be continuously tuned by adjusting the amount of carboxylate modifier. This property was attributed to the selective decrease in the hydroxyl adsorption affinity of the manganese oxides by the adsorbed carboxylate groups. The selectivity enhancement is not affected by the tail structure of the carboxylic acid.