Dopant- and Surfactant-Tuned Electrode–Electrolyte Interface Enabling Efficient Alkynol Semi-Hydrogenation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(11), P. 6516 - 6525

Published: March 13, 2023

Electrochemical alkynol semi-hydrogenation has emerged as a sustainable and environmentally benign route for the production of high-value alkenols, featuring water hydrogen source instead H2. It is highly challenging to design electrode-electrolyte interface with efficient electrocatalysts their matched electrolytes break selectivity-activity stereotype. Here, boron-doped Pd catalysts (PdB) surfactant-modified are proposed enable simultaneous increase in alkenol selectivity conversion. Typically, compared pure commercial Pd/C catalysts, PdB catalyst achieves both higher turnover frequency (139.8 h-1) specific (above 90%) 2-methyl-3-butyn-2-ol (MBY). Quaternary ammonium cationic surfactants that employed electrolyte additives assembled at electrified response applied bias potential, establishing an interfacial microenvironment can facilitate transfer hinder suitably. Eventually evolution reaction inhibited promoted, without inducing decrease selectivity. This work offers distinct perspective on creating suitable electrosynthesis.

Language: Английский

---

Electrochemical hydrogenation and oxidation of organic species involving water

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(4), P. 277 - 293

Published: March 25, 2024

Language: Английский

---

Renewable energy driven electroreduction nitrate to ammonia and in-situ ammonia recovery via a flow-through coupled device

Water Research, Journal Year: 2023, Volume and Issue: 242, P. 120256 - 120256

Published: June 20, 2023

Language: Английский

---

Designed Nanomaterials for Electrocatalytic Organic Hydrogenation Using Water as the Hydrogen Source

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(13), P. 1872 - 1883

Published: June 14, 2023

ConspectusThe hydrogenation reaction is one of the most frequently used transformations in organic synthesis. Electrocatalytic by using water (H2O) as hydrogen source offers an efficient and sustainable approach to synthesize hydrogenated products under ambient conditions. Such a technique can avoid use high-pressure flammable gas or other toxic/expensive donors, which usually cause environmental, safety, cost concerns. Interestingly, utilizing easily available heavy (D2O) for deuterated syntheses also attractive due widespread applications molecules synthesis pharmaceutical industry. Despite impressive achievements, electrode selection mainly relies on trial-and-error modes, how electrodes dictate outcomes remains elusive. Therefore, rational design nanostructured driving electrocatalytic series organics via H2O electrolysis developed.In this Account, we review recent advances different types functional groups, including C≡C, C≡N, C═C, C═O, C-Br/I bonds, -NO2, N-heterocycles, with over cathodes. First, general steps (reactant/intermediate adsorption, active atomic (H*) formation, surface reaction, product desorption) are analyzed, key factors proposed optimize performance (e.g., selectivity, activity, Faradaic efficiency (FE), rate, productivity) inhibit side reactions. Then, ex situ spectroscopic tools study intermediates interpret mechanisms introduced. Third, based knowledge mechanisms, introduce catalyst principles detail adoption reactants intermediates, promote formation H* from electrolysis, evolution reactions, improve FEs, space-time productivity products. We then some typical examples. (i) P- S-modified Pd decrease C═C adsorption enabling semihydrogenation alkynes high selectivity FEs at lower potentials. creating high-curvature nanotips concentrate substrates further speeds up process. (ii) By introducing low-coordination sites into Fe combining fluorine modify Co facilitate nitriles N-heterocycles activity obtained. (iii) forming isolated induce specific σ-alkynyl steering S vacancies Co3S4-x preferentially adsorb reduced group-decorated nitroarenes chemoselectivity realized. (iv) For reactant participated designing hydrophobic diffusion layer-supported ultrasmall Cu nanoparticles enhance mass transfer, activation, H2 ethylene ampere-level production 97.7% FE accomplished. Finally, provide outlook current challenges promising opportunities area. believe that summarized here paradigm highly selective nanomaterials achieve fascinating performances.

Language: Английский

---

Unveiling the structural transformation and activity origin of heteroatom-doped carbons for hydrogen evolution

Proceedings of the National Academy of Sciences, Journal Year: 2023, Volume and Issue: 120(20)

Published: May 8, 2023

Heteroatom-doped carbon materials have been widely used in many electrocatalytic reduction reactions. Their structure-activity relationships are mainly explored based on the assumption that doped remain stable during electrocatalysis. However, structural evolution of heteroatom-doped is often ignored, and their active origins still unclear. Herein, taking N-doped graphite flake (N-GP) as research model, we present hydrogenation both N C atoms consequent reconstruction skeleton hydrogen reaction (HER), accompanied by a remarkable promotion HER activity. The dopants gradually hydrogenated almost completely dissolved form ammonia. Theoretical simulations demonstrate species leads to from hexagonal 5,7-topological rings (G5-7) with thermoneutral adsorption easy water dissociation. P-, S-, Se-doped graphites also show similar removal heteroatoms formation G5-7 rings. Our work unveils activity origin toward opens door rethinking structure-performance carbon-based for other

Language: Английский

---

Recent progress in advanced catalysts for electrocatalytic hydrogenation of organics in aqueous conditions

eScience, Journal Year: 2023, Volume and Issue: 3(5), P. 100156 - 100156

Published: June 17, 2023

Electrocatalytic hydrogenation (ECH) of organics using water as hydrogen donors has been regarded a green organic reduction technique to replace traditional chemical reactions that use sacrificial chemicals. The development ECH process provides potential applications in the production value-added chemicals owing its low energy consumption, pollution, high safety, and superior sustainability. However, application is limited by conversion rate poor selectivity toward desired products. efficiency can be improved rational design electrocatalysts. This review covers several representative electrocatalytic systems (aldehydes, ketones, phenolic organics, alkynes, organonitrogen compounds) summarizes different mechanisms, followed thorough discussion on modification strategies electrocatalysts are currently adopted enhance catalytic performance. Finally, view current challenges for ECH, we discuss possible future directions field, aiming provide guidance catalyst highly efficient over feedstocks.

Language: Английский

---

Recent Progress on Computation‐Guided Catalyst Design for Highly Efficient Nitrogen Reduction Reaction

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(34)

Published: April 5, 2024

Abstract Electrochemical nitrogen reduction reaction (NRR) for ammonia synthesis has attracted great interest in recent years, which presents a carbon‐free alternative to the energy‐intensive Haber–Bosch process. Besides, NRR also provides promising coverage route of renewable energy since NH 3 is considered second generation hydrogen while possessing established technologies liquefaction, storage, and transport. However, there are long‐term challenges catalyst design due its low intrinsic activity unsatisfied selectivity. Fortunately, by conducting extensive explorations this field, much progress achieved boosting performance. Herein, from view atomic/electronic level, three promotion effects summarized (i.e., electron effect, geometry ligand effect), tackle Representative studies with taking fully advantages reviewed, realized remarkable Finally, future research directions prospects discussed. It highly expected that review will enable advancement catalysts promote further development electrochemical NRR.

Language: Английский

---

Earthworm‐Inspired Co/Co₃O₄/CoF₂@NSC Nanofibrous Electrocatalyst with Confined Channels for Enhanced ORR/OER Performance

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(26)

Published: Feb. 20, 2024

Abstract The rational construction of highly active and durable oxygen‐reactive electrocatalysts for oxygen reduction/evolution reaction (ORR/OER) plays a critical role in rechargeable metal‐air batteries. It is pivotal to achieve optimal utilization electrocatalytically sites valid control the high specific internal surface area. Inspiration designing can come from nature, as it full precisely manipulated efficient structures. Herein, inspired by earthworms fertilizing soil, 3D carbon nanofibrous electrocatalyst with multiple interconnected nanoconfined channels, cobalt‐based heterojunction particles enriched N, S heteroatoms (Co/Co 3 O 4 /CoF 2 @NSC confined channels) rationally designed, showing superior bifunctional electrocatalytic activity alkaline electrolyte, even outperforming that benchmark Pt/C‐RuO catalyst. This work demonstrates new method porous structural regulation, which channels within nanofibers are controllably formed spontaneous migration nanoparticles under CO atmosphere. Theoretical analysis reveals constructing Co/Co greatly adjust electron distribution, effectively lower barrier inter‐mediate reduce OER/ORR overpotential. introduces novel nature‐inspired strategy well‐designed architectures.

Language: Английский

---

Rh-dispersed Cu nanowire catalyst for boosting electrocatalytic hydrogenation of 5-hydroxymethylfurfural

Science Bulletin, Journal Year: 2023, Volume and Issue: 68(19), P. 2190 - 2199

Published: July 25, 2023

Language: Английский

---

High Performance Polyoxometalate-Stabilizing Pt Nanocatalysts for Quinoline Hydrogenation with Water-Mediated Dynamic Hydrogen

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 5344 - 5355

Published: March 26, 2024

In this work, a Keggin-type platinum substituted polyoxometalate (POM) is constructed by the reaction of monolacunary phosphotungstate precursor [PW11O39]7– with chloroplatinic acid. The as-obtained tetrabutylammonium salt (TBA-PWPt) demonstrates that dimeric Pt2+ ions are incorporated into POM frameworks and linked two anions. Notably, once Pt-substituted anion reduced H2, anion-stabilizing Pt nanocatalysts generated, which greatly facilitates forming oxygen vacancies adjacent to Pt0 species. show superior catalytic activity stability for selective hydrogenation quinoline 1,2,3,4-tetrahydroquinoline in water. Detailed investigations elucidate stronger adsorption on surface H2 activated at POMs-Pt interface site. Moreover, density functional theory (DFT) calculations H2O adsorbed interfacial then undergoes homolytic dissociation produce hydroxyl group (OH–) hydride (H–) H– species transferred N-containing pyridine ring hydrogenation, OH– help promote heterolytic H+ Sequentially, produced proton groups generate H2O, cycle completed.

Language: Английский

---