A flexible, redox-active macrocycle enables the electrocatalytic reduction of nitrate to ammonia by a cobalt complexElectronic supplementary information (ESI) available. CCDC 1823665 and 1823666. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc00721g

A flexible, redox-active macrocycle enables the electrocatalytic reduction of nitrate to ammonia... The cobalt macrocycle complex [Co(DIM)Br2]+ (DIM = 2,3-dimethyl-1,4,8,11-tetraazacyclotetradeca-1,3-diene) is an electrocatalyst for the selective reduction of nitrate to ammonia in aqueous solution. The catalyst operates over a wide pH range and with very high faradaic efficiency, albeit with large overpotential. Experimental investigations, supported by electronic structure calculations, reveal that catalysis commences when nitrate binds to the two-electron reduced species CoII(DIM), where cobalt and the macrocycle are each reduced by a single electron. Several mechanisms for the initial reduction of nitrate to nitrite were explored computationally and found to be feasible at room temperature. The reduced DIM ligand plays an important role in these mechanisms by directly transferring a single electron to the bound nitrate substrate, activating it for further reactions. These studies further reveal that the DIM macrocycle is critical to nitrate reduction, specifically its combination of redox non-innocence, hydrogen-bonding functionality and flexibility in coordination mode. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Chemical Science Royal Society of Chemistry

A flexible, redox-active macrocycle enables the electrocatalytic reduction of nitrate to ammonia by a cobalt complexElectronic supplementary information (ESI) available. CCDC 1823665 and 1823666. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc00721g

Loading next page...
 
/lp/rsc/a-flexible-redox-active-macrocycle-enables-the-electrocatalytic-Ki3ndnGA5M
Publisher
Royal Society of Chemistry
Copyright
This journal is © The Royal Society of Chemistry
ISSN
2041-6520
D.O.I.
10.1039/c8sc00721g
Publisher site
See Article on Publisher Site

Abstract

The cobalt macrocycle complex [Co(DIM)Br2]+ (DIM = 2,3-dimethyl-1,4,8,11-tetraazacyclotetradeca-1,3-diene) is an electrocatalyst for the selective reduction of nitrate to ammonia in aqueous solution. The catalyst operates over a wide pH range and with very high faradaic efficiency, albeit with large overpotential. Experimental investigations, supported by electronic structure calculations, reveal that catalysis commences when nitrate binds to the two-electron reduced species CoII(DIM), where cobalt and the macrocycle are each reduced by a single electron. Several mechanisms for the initial reduction of nitrate to nitrite were explored computationally and found to be feasible at room temperature. The reduced DIM ligand plays an important role in these mechanisms by directly transferring a single electron to the bound nitrate substrate, activating it for further reactions. These studies further reveal that the DIM macrocycle is critical to nitrate reduction, specifically its combination of redox non-innocence, hydrogen-bonding functionality and flexibility in coordination mode.

Journal

Chemical ScienceRoyal Society of Chemistry

Published: May 23, 2018

There are no references for this article.

You’re reading a free preview. Subscribe to read the entire article.


DeepDyve is your
personal research library

It’s your single place to instantly
discover and read the research
that matters to you.

Enjoy affordable access to
over 18 million articles from more than
15,000 peer-reviewed journals.

All for just $49/month

Explore the DeepDyve Library

Search

Query the DeepDyve database, plus search all of PubMed and Google Scholar seamlessly

Organize

Save any article or search result from DeepDyve, PubMed, and Google Scholar... all in one place.

Access

Get unlimited, online access to over 18 million full-text articles from more than 15,000 scientific journals.

Your journals are on DeepDyve

Read from thousands of the leading scholarly journals from SpringerNature, Elsevier, Wiley-Blackwell, Oxford University Press and more.

All the latest content is available, no embargo periods.

See the journals in your area

DeepDyve

Freelancer

DeepDyve

Pro

Price

FREE

$49/month
$360/year

Save searches from
Google Scholar,
PubMed

Create lists to
organize your research

Export lists, citations

Read DeepDyve articles

Abstract access only

Unlimited access to over
18 million full-text articles

Print

20 pages / month

PDF Discount

20% off