Matches in SemOpenAlex for { <https://semopenalex.org/work/W4382284347> ?p ?o ?g. }
- W4382284347 endingPage "19552" @default.
- W4382284347 startingPage "19540" @default.
- W4382284347 abstract "The production of ammonia for agricultural and energy demands has accelerated research for more environmentally-friendly synthesis options, particularly the electrocatalytic reduction of molecular nitrogen (nitrogen reduction reaction, NRR). Catalyst activity for NRR, and selectivity for NRR over the competitive hydrogen evolution reaction (HER), are critical issues for which fundamental knowledge remains scarce. Herein, we present results regarding the NRR activity and selectivity of sputter-deposited titanium nitride and titanium oxynitride films for NRR and HER. Electrochemical, fluorescence and UV absorption measurements show that titanium oxynitride exhibits NRR activity under acidic conditions (pH 1.6, 3.2) but is inactive at pH 7. Ti oxynitride is HER inactive at all these pH values. In contrast, TiN - with no oxygen content upon deposition - is both NRR and HER inactive at all the above pH values. This difference in oxynitride/nitride reactivity is observed despite the fact that both films exhibit very similar surface chemical compositions - predominantly TiIV oxide - upon exposure to ambient, as determined by ex situ X-ray photoelectron spectroscopy (XPS). XPS, with in situ transfer between electrochemical and UHV environments, however, demonstrates that this TiIV oxide top layer is unstable under acidic conditions, but stable at pH 7, explaining the inactivity of titanium oxynitride at this pH. The inactivity of TiN at acidic and neutral pH is explained by DFT-based calculations showing that N2 adsorption at N-ligated Ti centers is energetically significantly less favorable than at O-ligated centers. These calculations also predict that N2 will not bind to TiIV centers due to a lack of π-backbonding. Ex situ XPS measurements and electrochemical probe measurements at pH 3.2 demonstrate that Ti oxynitride films undergo gradual dissolution under NRR conditions. The present results demonstrate that the long-term catalyst stability and maintenance of metal cations in intermediate oxidation states for pi-backbonding are critical issues worthy of further examination." @default.
- W4382284347 created "2023-06-28" @default.
- W4382284347 creator A5007169587 @default.
- W4382284347 creator A5015055814 @default.
- W4382284347 creator A5021047497 @default.
- W4382284347 creator A5030200062 @default.
- W4382284347 creator A5062868414 @default.
- W4382284347 creator A5067710353 @default.
- W4382284347 creator A5072046677 @default.
- W4382284347 creator A5081902567 @default.
- W4382284347 creator A5089967637 @default.
- W4382284347 creator A5092280567 @default.
- W4382284347 date "2023-01-01" @default.
- W4382284347 modified "2023-10-16" @default.
- W4382284347 title "Stability and Activity of Titanium Oxynitride Thin Films for the Electrocatalytic Reduction of Molecular Nitrogen to Ammonia at Different pH Values" @default.
- W4382284347 cites W1979544533 @default.
- W4382284347 cites W2001611094 @default.
- W4382284347 cites W2020023668 @default.
- W4382284347 cites W2036113194 @default.
- W4382284347 cites W2098547240 @default.
- W4382284347 cites W2121817924 @default.
- W4382284347 cites W2122343893 @default.
- W4382284347 cites W2140168076 @default.
- W4382284347 cites W2225723597 @default.
- W4382284347 cites W2512841610 @default.
- W4382284347 cites W2740562083 @default.
- W4382284347 cites W2803544914 @default.
- W4382284347 cites W2803729875 @default.
- W4382284347 cites W2897484911 @default.
- W4382284347 cites W2906749653 @default.
- W4382284347 cites W2912850146 @default.
- W4382284347 cites W2913722398 @default.
- W4382284347 cites W2914367192 @default.
- W4382284347 cites W2932681421 @default.
- W4382284347 cites W2946566464 @default.
- W4382284347 cites W2960512769 @default.
- W4382284347 cites W2964028581 @default.
- W4382284347 cites W2992272344 @default.
- W4382284347 cites W3016473822 @default.
- W4382284347 cites W3030589897 @default.
- W4382284347 cites W3094269193 @default.
- W4382284347 cites W3097613090 @default.
- W4382284347 cites W3113090012 @default.
- W4382284347 cites W3125003251 @default.
- W4382284347 cites W3129028199 @default.
- W4382284347 cites W3132735435 @default.
- W4382284347 cites W3161551980 @default.
- W4382284347 cites W3161603852 @default.
- W4382284347 cites W3214718597 @default.
- W4382284347 cites W4200512939 @default.
- W4382284347 cites W4295338042 @default.
- W4382284347 cites W4313406148 @default.
- W4382284347 cites W4313490370 @default.
- W4382284347 doi "https://doi.org/10.1039/d3cp01330h" @default.
- W4382284347 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/37395083" @default.
- W4382284347 hasPublicationYear "2023" @default.
- W4382284347 type Work @default.
- W4382284347 citedByCount "0" @default.
- W4382284347 crossrefType "journal-article" @default.
- W4382284347 hasAuthorship W4382284347A5007169587 @default.
- W4382284347 hasAuthorship W4382284347A5015055814 @default.
- W4382284347 hasAuthorship W4382284347A5021047497 @default.
- W4382284347 hasAuthorship W4382284347A5030200062 @default.
- W4382284347 hasAuthorship W4382284347A5062868414 @default.
- W4382284347 hasAuthorship W4382284347A5067710353 @default.
- W4382284347 hasAuthorship W4382284347A5072046677 @default.
- W4382284347 hasAuthorship W4382284347A5081902567 @default.
- W4382284347 hasAuthorship W4382284347A5089967637 @default.
- W4382284347 hasAuthorship W4382284347A5092280567 @default.
- W4382284347 hasConcept C118792377 @default.
- W4382284347 hasConcept C127413603 @default.
- W4382284347 hasConcept C147789679 @default.
- W4382284347 hasConcept C150394285 @default.
- W4382284347 hasConcept C161790260 @default.
- W4382284347 hasConcept C17525397 @default.
- W4382284347 hasConcept C175708663 @default.
- W4382284347 hasConcept C178790620 @default.
- W4382284347 hasConcept C179104552 @default.
- W4382284347 hasConcept C185592680 @default.
- W4382284347 hasConcept C42360764 @default.
- W4382284347 hasConcept C506065880 @default.
- W4382284347 hasConcept C525849907 @default.
- W4382284347 hasConcept C52859227 @default.
- W4382284347 hasConcept C537208039 @default.
- W4382284347 hasConcept C55904794 @default.
- W4382284347 hasConceptScore W4382284347C118792377 @default.
- W4382284347 hasConceptScore W4382284347C127413603 @default.
- W4382284347 hasConceptScore W4382284347C147789679 @default.
- W4382284347 hasConceptScore W4382284347C150394285 @default.
- W4382284347 hasConceptScore W4382284347C161790260 @default.
- W4382284347 hasConceptScore W4382284347C17525397 @default.
- W4382284347 hasConceptScore W4382284347C175708663 @default.
- W4382284347 hasConceptScore W4382284347C178790620 @default.
- W4382284347 hasConceptScore W4382284347C179104552 @default.
- W4382284347 hasConceptScore W4382284347C185592680 @default.
- W4382284347 hasConceptScore W4382284347C42360764 @default.
- W4382284347 hasConceptScore W4382284347C506065880 @default.
- W4382284347 hasConceptScore W4382284347C525849907 @default.