We report novel structureactivity relationships and explore the chemical state and structure of catalytically active sites under operando conditions during the electrochemical CO2 reduction reaction (CO2RR) catalyzed by a series of porous ironnitrogencarbon (FeNC) catalysts. The FeNC catalysts were synthesized from different nitrogen precursors and, as a result of this, exhibited quite distinct physical properties, such as BET surface areas and distinct chemical N-functionalities in varying ratios. The chemical diversity of the FeNC catalysts was harnessed to set up correlations between the catalytic CO2RR activity and their chemical nitrogen-functionalities, which provided a deeper understanding between catalyst chemistry and function. XPS measurements revealed a dominant role of porphyrin-like FeNx motifs and pyridinic nitrogen species in catalyzing the overall reaction process. Operando EXAFS measurements revealed an unexpected change in the Fe oxidation state and associated coordination from Fe2+ to Fe1+. This redox change coincides with the onset of catalytic CH4 production around 0.9 VRHE. The ability of the solid state coordinative Fe1+Nx moiety to form hydrocarbons from CO2 is remarkable, as it represents the solid-state analogue to molecular Fe1+ coordination compounds with the same catalytic capability under homogeneous catalytic environments. This finding highlights a conceptual bridge between heterogeneous and homogenous catalysis and contributes significantly to our fundamental understanding of the FeNC catalyst function in the CO2RR.
Chemical Science – Royal Society of Chemistry
Published: May 18, 2018
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
Query the DeepDyve database, plus search all of PubMed and Google Scholar seamlessly
Save any article or search result from DeepDyve, PubMed, and Google Scholar... all in one place.
Get unlimited, online access to over 18 million full-text articles from more than 15,000 scientific journals.
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.
“Hi guys, I cannot tell you how much I love this resource. Incredible. I really believe you've hit the nail on the head with this site in regards to solving the research-purchase issue.”Daniel C.
“Whoa! It’s like Spotify but for academic articles.”@Phil_Robichaud
“I must say, @deepdyve is a fabulous solution to the independent researcher's problem of #access to #information.”@deepthiw
“My last article couldn't be possible without the platform @deepdyve that makes journal papers cheaper.”@JoseServera