Tailored catalyst microenvironments for CO2 electroreduction to multicarbon products on copper using bilayer ionomer coatings

Nature Energy, Journal Year: 2021, Volume and Issue: 6(11), P. 1026 - 1034

Published: Oct. 28, 2021

Language: Английский

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Construction of C–N bonds from small-molecule precursors through heterogeneous electrocatalysis

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(5), P. 303 - 319

Published: April 25, 2022

Language: Английский

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Engineering Catalyst–Electrolyte Microenvironments to Optimize the Activity and Selectivity for the Electrochemical Reduction of CO₂ on Cu and Ag

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(4), P. 484 - 494

Published: Feb. 1, 2022

ConspectusThe electrochemical reduction of carbon dioxide (CO2R) driven by renewably generated electricity (e.g., solar and wind) offers a promising means for reusing the CO2 released during production cement, steel, aluminum as well ammonia methanol. If could be removed from atmosphere at acceptable costs (i.e., <$100/t CO2), then CO2R used to produce carbon-containing chemicals fuels in fully sustainable manner. Economic considerations dictate that current densities must range 0.1 1 A/cm2 selectivity toward targeted product high order minimize separation costs. Industrially relevant operating conditions can achieved using gas diffusion electrodes (GDEs) maximize transport species cathode combining such with solid-electrolyte membrane eliminating ohmic losses associated liquid electrolytes. Additionally, attained careful tuning microenvironment near catalyst surface pH, concentrations H2O, identities cations double layer adjacent surface).We begin this Account discussion our experimental theoretical work aimed optimizing microenvironments CO2R. We first examine effects morphology on multicarbon (C2+) products over Cu-based catalysts explore role mass transfer combined kinetics buffer reactions local concentration pH surface. This is followed dependence dynamics formation specific both Cu Ag catalysts. Next, we impact electrolyte cation identity rate distribution products. Subsequently, look utilizing pulsed electrolysis tune The last part demonstrates ionomer-coated combination enable attainment very (>90%) C2+ an aqueous electrolyte. extended consider difference catalyst–nanoparticle microenvironment, present electrode assembly (MEA), respect planar immersed

Language: Английский

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Emerging Electrochemical Processes to Decarbonize the Chemical Industry

JACS Au, Journal Year: 2022, Volume and Issue: 2(5), P. 1054 - 1070

Published: May 3, 2022

Electrification is a potential approach to decarbonizing the chemical industry. Electrochemical processes, when they are powered by renewable electricity, have lower carbon footprints in comparison conventional thermochemical routes. In this Perspective, we discuss electrochemical routes for production and provide our views on how processes can be matured academic research laboratories future industrial applications. We first analyze CO2 emission manufacturing industry conduct survey of state art electrosynthesis methods three most emission-intensive areas: petrochemical production, nitrogen compound metal smelting. Then, identify technical bottlenecks electrifying productions from both chemistry engineering perspectives propose strategies tackle these issues. Finally, reduce emissions with hope inspire more efforts manufacturing.

Language: Английский

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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

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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

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Recent Advances in Electrocatalytic Hydrogenation Reactions on Copper‐Based Catalysts

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(14)

Published: Sept. 27, 2023

Hydrogenation reactions play a critical role in the synthesis of value-added products within chemical industry. Electrocatalytic hydrogenation (ECH) using water as hydrogen source has emerged an alternative to conventional thermocatalytic processes for sustainable and decentralized under mild conditions. Among various ECH catalysts, copper-based (Cu-based) nanomaterials are promising candidates due their earth-abundance, unique electronic structure, versatility, high activity/selectivity. Herein, recent advances application Cu-based catalysts upgrading valuable chemicals systematically analyzed. The properties initially introduced, followed by design strategies enhance activity selectivity. Then, typical on presented detail, including carbon dioxide reduction multicarbon generation, alkyne-to-alkene conversion, selective aldehyde ammonia production from nitrogen-containing substances, amine organic nitrogen compounds. In these catalyst composition nanostructures toward different is focused. co-hydrogenation two substrates (e.g., CO

Language: Английский

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Atom-level interaction design between amines and support for achieving efficient and stable CO2 capture

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 13, 2024

Abstract Amine-functionalized adsorbents offer substantial potential for CO 2 capture owing to their selectivity and diverse application scenarios. However, effectiveness is hindered by low efficiency unstable cyclic performance. Here we introduce an amine-support system designed achieve efficient stable capture. Through atom-level design, each polyethyleneimine (PEI) molecule precisely impregnated into the cage-like pore of MIL–101(Cr), forming composites via strong coordination with unsaturated Cr acid sites within crystal lattice. The resulting adsorbent demonstrates a regeneration energy (39.6 kJ/mol CO2 ), excellent stability (0.18% decay per cycle under dry regeneration), high adsorption capacity (4.0 mmol/g), rapid kinetics (15 min saturation at 30 °C). These properties stem from unique electron-level interaction between amine support, effectively preventing carbamate products’ dehydration. This work presents feasible promising cost-effective sustainable strategy.

Language: Английский

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Regulating Surface Reaction Kinetics through Ligand Field Effects for Fast and Reversible Aqueous Zinc Batteries

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(44)

Published: Sept. 9, 2022

Abstract Designing water‐deficient solvation sheath of Zn 2+ by ligand substitution is a widely used strategy to protect metal anode, yet the intrinsic tradeoff between nucleation/dissolution kinetics and side hydrogen evolution reaction (HER) remains huge challenge. Herein, we find boric acid (BA) with moderate field interaction can partially replace H 2 O molecules in , forming stable sheath. It enables fast substantially suppressed HER. Crucially, systematically comparing strength energies BA ever‐reported electrolyte additives, also that energy has strong correlation HER inhibition ability, displaying classic volcano behavior. The modulation map could provide valuable insights for design zinc batteries beyond.

Language: Английский

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σ-Alkynyl Adsorption Enables Electrocatalytic Semihydrogenation of Terminal Alkynes with Easy-Reducible/Passivated Groups over Amorphous PdS_x Nanocapsules

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(42), P. 19456 - 19465

Published: Oct. 5, 2022

Highly chemo- and regioselective semihydrogenation of alkynes is significant challenging for the synthesis functionalized alkenes. Here, a sequential self-template method used to synthesize amorphous palladium sulfide nanocapsules (PdSx ANCs), which enables electrocatalytic terminal in H2O with excellent tolerance easily reducible groups (e.g., C–I/Br/Cl, C═O) metal center deactivating skeletons quinolyl, carboxyl, nitrile). Mechanistic studies demonstrate that specific σ-alkynyl adsorption via carbon negligible alkene on isolated Pd2+ sites ensure successful various alkenes outstanding time-irrelevant selectivity wide potential range. The key hydrogen radical intermediates are validated by electron paramagnetic resonance high-resolution mass spectrometry. Gram-scale 4-bromostyrene expedient preparation deuterated precursors drugs D2O show promising applications. Impressively, PdSx ANCs can be applied prevailing thermocatalytic alkyne using H2.

Language: Английский

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