Pre‐Activation of CO2 at Cobalt Phthalocyanine‐Mg(OH)2 Interface for Enhanced Turnover Rate DOI
Fenglei Lyu,

Bingyun Ma,

Xulan Xie

et al.

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(26)

Published: March 21, 2023

Abstract Cobalt phthalocyanine (CoPc) anchored on heterogeneous scaffold has drawn great attention as promising electrocatalyst for carbon dioxide reduction reaction (CO 2 RR), but the molecule/substrate interaction is still pending clarification and optimization to maximize kinetics. Herein, a CO RR catalyst fabricated by affixing CoPc onto Mg(OH) substrate primed with conductive carbon, demonstrating an ultra‐low overpotential of 0.31 ± 0.03 V at 100 mA cm −2 high faradaic efficiency >95% wide current density range production, well heavy‐duty operation more than 50 h in membrane electrode assembly. Mechanistic investigations employing situ Raman attenuated total reflection surface‐enhanced infrared absorption spectroscopy unravel that plays pivotal role enhance kinetics facilitating first‐step electron transfer form anionic *CO − intermediates. DFT calculations further elucidate introducing Lewis acid sites help polarize molecules absorbed metal centers consequently lower activation barrier. This work signifies tailoring catalyst‐support interface molecular level enhancing turnover rate RR.

Language: Английский

Electrocatalysis with Molecular Transition-Metal Complexes for Reductive Organic Synthesis DOI Creative Commons
Nicolas Kaeffer, Walter Leitner

JACS Au, Journal Year: 2022, Volume and Issue: 2(6), P. 1266 - 1289

Published: May 31, 2022

Electrocatalysis enables the formation or cleavage of chemical bonds by a genuine use electrons holes from an electrical energy input. As such, electrocatalysis offers resource-economical alternative pathways that bypass sacrificial, waste-generating reagents often required in classical thermal redox reactions. In this Perspective, we showcase exploitation molecular electrocatalysts for electrosynthesis, particular reductive conversion organic substrates. Selected case studies illustrate efficient not only are appropriate shuttles but also embrace features organometallic catalysis to facilitate and control steps. From these examples, guidelines proposed design suited reduction We finally expose opportunities brought catalyzed electrosynthesis functionalize backbones, namely using sustainable building blocks.

Language: Английский

Citations

39
Advances in CO2 activation by frustrated Lewis pairs: from stoichiometric to catalytic reactions DOI Creative Commons
Md. Nasim Khan, Yara van Ingen,

Tribani Boruah

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(47), P. 13661 - 13695

Published: Jan. 1, 2023

Frustrated Lewis pair systems have been explored efficiently in homogeneous and heterogeneous conditions for the activation reduction of CO 2 to various useful products stoichiometric as well catalytic reactions.

Language: Английский

Citations

31
Nanoengineering of metal-based electrocatalysts for carbon dioxide (CO2) reduction: A critical review DOI
Sina Pourebrahimi, Majid Pirooz,

Shabnam Ahmadi

et al.

Materials Today Physics, Journal Year: 2023, Volume and Issue: 38, P. 101250 - 101250

Published: Oct. 6, 2023

Language: Английский

Citations

30
Boosting CO 2 photoreduction by π–π-induced preassembly between a Cu(I) sensitizer and a pyrene-appended Co(II) catalyst DOI Creative Commons
Jia‐Wei Wang, Zizi Li,

Zhi‐Mei Luo

et al.

Proceedings of the National Academy of Sciences, Journal Year: 2023, Volume and Issue: 120(13)

Published: March 21, 2023

The design of a highly efficient system for CO 2 photoreduction fully based on earth-abundant elements presents challenge, which may be overcome by installing suitable interactions between photosensitizer and catalyst to expedite the intermolecular electron transfer. Herein, we have designed pyrene-decorated Cu(I) complex with rare dual emission behavior, aiming at additional π-interaction pyrene-appended Co(II) visible light–driven -to-CO conversion. results 1 H NMR titration, time-resolved fluorescence/absorption spectroscopies, quantum chemical simulations, photocatalytic experiments clearly demonstrate that dynamic π–π interaction sensitizer is advantageous in photocatalysis accelerating transfer rate up 6.9 × 10 5 s −1 , thus achieving notable apparent yield 19% 425 nm near-unity selectivity. While comparable most molecular systems, this value over three times pyrene-free (6.0%) far surpassing benchmarking Ru(II) tris(bipyridine) (0.3%) Ir(III) tris(2-phenylpyridine) (1.4%) photosensitizers under parallel conditions.

Language: Английский

Citations

25
Pre‐Activation of CO2 at Cobalt Phthalocyanine‐Mg(OH)2 Interface for Enhanced Turnover Rate DOI
Fenglei Lyu,

Bingyun Ma,

Xulan Xie

et al.

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(26)

Published: March 21, 2023

Abstract Cobalt phthalocyanine (CoPc) anchored on heterogeneous scaffold has drawn great attention as promising electrocatalyst for carbon dioxide reduction reaction (CO 2 RR), but the molecule/substrate interaction is still pending clarification and optimization to maximize kinetics. Herein, a CO RR catalyst fabricated by affixing CoPc onto Mg(OH) substrate primed with conductive carbon, demonstrating an ultra‐low overpotential of 0.31 ± 0.03 V at 100 mA cm −2 high faradaic efficiency >95% wide current density range production, well heavy‐duty operation more than 50 h in membrane electrode assembly. Mechanistic investigations employing situ Raman attenuated total reflection surface‐enhanced infrared absorption spectroscopy unravel that plays pivotal role enhance kinetics facilitating first‐step electron transfer form anionic *CO − intermediates. DFT calculations further elucidate introducing Lewis acid sites help polarize molecules absorbed metal centers consequently lower activation barrier. This work signifies tailoring catalyst‐support interface molecular level enhancing turnover rate RR.

Language: Английский

Citations

23