Thiol treatment tunes interfacial wettability for electrochemical alkynol semi‐hydrogenation DOI Open Access

Xingzhou Zha,

Yuan Zhao, Hongliang Jiang

et al.

AIChE Journal, Journal Year: 2024, Volume and Issue: 70(12)

Published: Aug. 23, 2024

Abstract Electrocatalytic semi‐hydrogenation of alkynols holds tremendous advantages over conventional thermocatalysis process. However, the selectivity‐activity seesaw effect is a principal obstacle to its further development. Inspired by interfacial self‐assembled monolayers, alkanethiols with different alkyl chain lengths are employed modify Cu surface for controllably modulating activity and selectivity in alkynols. 1‐dodecanethiol‐modified nanowires (Cu NWs) exhibit optimal electrosynthesis 2‐methyl‐3‐buten‐2‐ol excellent specific (above 93%) 2‐methyl‐3‐butyn‐2‐ol. Mechanistic studies reveal that proportion liquid‐like water increases while isolated reduces at hydrophobic interface. Moreover, we assemble larger 3 × 100 cm 2 electrolyzer stack, which can deliver single‐pass alkynol conversion rate 95% an alkenol 94% 15 A stack current. Eventually, NWs catalyst thiol treatment also applicable various unsaturated

Language: Английский

Developing electrochemical hydrogenation towards industrial application DOI
Julian T. Kleinhaus, Jonas Wolf, Kevinjeorjios Pellumbi

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(21), P. 7305 - 7332

Published: Jan. 1, 2023

Electrochemical hydrogenation reactions hold the promise of more sustainable production routes for towards bulk and fine chemicals. Their broad applicability, reactor concepts, achieved milestones future perspectives are described herein.

Language: Английский

Citations

43
Promoting Electrocatalytic Semihydrogenation of Alkynols to Alkenols over a Bimetallic CuAu Alloy Catalyst DOI

Qinghui Ren,

Leilei Hao,

Jiangrong Yang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 5675 - 5684

Published: April 1, 2024

Electrocatalytic semihydrogenation of alkynols to alkenols under ambient conditions using H2O as a hydrogen source is highly attractive in synthetic chemistry. However, it still challenging achieve high Faradaic efficiency (FE) wide potential window. Herein, we reported bimetallic Cu3Au alloy an efficient catalyst for electrocatalytic alkenols. Specifically, during 2-butyne-1,4-diol (BYD) 2-butene-1,4-diol (BED), the achieves 12.6-fold greater reaction rate and higher FE compared with pure Cu (99 vs 63%). Moreover, maintains >96% FEs window from −0.19 −0.59 V RHE. We demonstrate that competitive adsorptions reactive (H*) BYD greatly influence processes. The presence Au facilitates H* formation reduces adsorption on Cu, thus enhancing hydrogenation performance. affords broad substrate scope aromatic alkynes, producing corresponding alkenes good selectivities. Finally, coupled glycerol oxidation replace oxygen evolution two-electrode system, showing 40% energy saving at 200 mA BED production coproduction valuable formate anode, demonstrating economical manner.

Language: Английский

Citations

10
A Cosolvent Electrolyte Boosting Electrochemical Alkynol Semihydrogenation DOI
Yuan Zhao,

Jia Wang,

Xingzhou Zha

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(2), P. 1938 - 1947

Published: Jan. 2, 2025

Green electricity-driven alkenol electrosynthesis via electrocatalytic alkynol semihydrogenation represents a sustainable route to conventional thermocatalysis. Both the electrocatalyst and electrolyte strongly impact performance. Despite significant progress in developing sophisticated electrocatalysts, well-designed conjunction with industrial catalysts is an attractive strategy advance industrialization process of semihydrogenation, but remains unexplored. Here, we develop dimethyl sulfoxide (DMSO)-H2O cosolvent for semihydrogenation. At conversion about 100%, DMSO-H2O compared DMSO-free counterpart enables selectivity on Cu be promoted from 60–70% over 90% at all measured current densities; meanwhile, reaction rate slightly decreased due inhibited water dissociation. Mechanistic studies reveal that strong hydrogen-bond interactions between DMSO H2O suppress dissociation interfacial H2O, leading H* coverage electrode surface. The hinders overhydrogenation alkynols favors production alkenols. Remarkably, DMSO-induced enhancement applicable set commercial various alkynols. Eventually, scaled-up 3 × 100 cm2 electrolyzer stack established achieve ∼96% ∼95% electrolyte. This work not only presents boosting electrosynthesis, also highlights possibility electro-production.

Language: Английский

Citations

0
Efficient Photocatalytic Semihydrogenation of 2-Butyne-1,4-diol over TiO2 Supported Cu Single Atoms with Near-Unity Conversion and Selectivity DOI
Zhenpeng Liu,

Zhipeng Ren,

Jinjin Li

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Language: Английский

Citations

0
Renaissance in Alkyne Semihydrogenation: Mechanism, Selectivity, Functional Group Tolerance, and Applications in Organic Synthesis DOI
Rafał Kusy, Karol Grela

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: April 25, 2025

Alkenes constitute a significant class of chemical compounds with applications in the bulk, pharmaceutical, or perfume industry. Among known methods olefin production, semihydrogenation C-C triple bond seems to be most straightforward one. Nonetheless, success this reaction requires full control over diastereoselectivity, eradication parasitic process over-reduction migration double formed, and achieving satisfactory functional-group compatibility. The review demonstrates developments field alkyne period 2010-2022, selected papers published 2023 2024, emphasizing solutions above-mentioned limitations. We discuss mechanistic aspects transformation, including those related unconventional systems. includes examples organic synthesis, confirming considerable utility process. Finally, strategies enhance catalyst selectivity are summarized. For reader's convenience, we provided graphical guidebook catalytic systems, illustrating efficiency particular method.

Language: Английский

Citations

0
Membrane‐Free Selective Semi‐Hydrogenation of Alkynes Over an In Situ Formed Copper Nanoparticle Electrode DOI
Pengyu Guo,

Yousen Xu,

Hao Bin Wu

et al.

Small, Journal Year: 2024, Volume and Issue: 20(33)

Published: March 26, 2024

Selective semi-hydrogenation of alkynes is a significant reaction for preparing functionalized alkenes. Electrochemical presents sustainable alternative to the traditional thermal process. In this research, affordable copper acetylacetonate employed as catalyst precursor electrocatalytic hydrogenation alkynes, using MeOH hydrogen source in an undivided cell. Good excellent yields both aromatic and aliphatic internal/terminal are obtained under constant current conditions. Notably, up 99% Z selectivity achieved various internal alkynes. Mechanistic investigations revealed formation nanoparticles (NPs) at cathode during electrolysis, acting selective semireduction The NPs deposited demonstrated reusable further hydrogenation.

Language: Английский

Citations

1
Electroplated Electrodes for Continuous and Mass‐Efficient Electrochemical Hydrogenation DOI Creative Commons
Jonas Wolf, Kevinjeorjios Pellumbi,

Sarankumar Haridas

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(18)

Published: Dec. 15, 2023

Abstract Electrocatalytic hydrogenations (ECH) enable the reduction of organic substrates upon usage electric current and present a sustainable alternative to conventional processes if green electricity is used. Opposed most protocols for electrode preparation, this work presents one‐step binder‐ additive‐free production silver‐ copper‐electroplated electrodes. Controlled adjustment preparation parameters allows tuning catalyst morphology its electrochemical properties. Upon optimization deposition protocol carbon support, high faradaic efficiencies 93 % ECH Vitamin A‐ E‐synthon 2‐methyl‐3‐butyn‐2‐ol (MBY) are achieved that can be maintained at densities 240 mA cm −2 minimal loadings 0.2 mg , corresponding an unmatched rate 1.47 kg MBE g cat −1 h . For continuous hydrogenation process, directly transferred into single‐pass operation mode giving 1.38 Subsequently, substrate spectrum was extended total 17 different C−C−, C−O− N−O−unsaturated compounds revealing general applicability reported process. Our results lay important groundwork development reactors electrodes able compete with palladium‐based thermocatalytic state art.

Language: Английский

Citations

2
Thiol treatment tunes interfacial wettability for electrochemical alkynol semi‐hydrogenation DOI Open Access

Xingzhou Zha,

Yuan Zhao, Hongliang Jiang

et al.

AIChE Journal, Journal Year: 2024, Volume and Issue: 70(12)

Published: Aug. 23, 2024

Abstract Electrocatalytic semi‐hydrogenation of alkynols holds tremendous advantages over conventional thermocatalysis process. However, the selectivity‐activity seesaw effect is a principal obstacle to its further development. Inspired by interfacial self‐assembled monolayers, alkanethiols with different alkyl chain lengths are employed modify Cu surface for controllably modulating activity and selectivity in alkynols. 1‐dodecanethiol‐modified nanowires (Cu NWs) exhibit optimal electrosynthesis 2‐methyl‐3‐buten‐2‐ol excellent specific (above 93%) 2‐methyl‐3‐butyn‐2‐ol. Mechanistic studies reveal that proportion liquid‐like water increases while isolated reduces at hydrophobic interface. Moreover, we assemble larger 3 × 100 cm 2 electrolyzer stack, which can deliver single‐pass alkynol conversion rate 95% an alkenol 94% 15 A stack current. Eventually, NWs catalyst thiol treatment also applicable various unsaturated

Language: Английский

Citations

0