Stability and activity of titanium oxynitride thin films for the electrocatalytic reduction of nitrogen to ammonia at different pH values DOI
Precious Chukwunenye,

Ashwin Ganesan,

Mojgan Gharaee

и другие.

Physical Chemistry Chemical Physics, Год журнала: 2023, Номер 25(29), С. 19540 - 19552

Опубликована: Янв. 1, 2023

The production of ammonia for agricultural and energy demands has accelerated research more environmentally-friendly synthesis options, particularly the electrocatalytic reduction molecular nitrogen (nitrogen reaction, NRR). Catalyst activity NRR, selectivity NRR over competitive hydrogen evolution reaction (HER), are critical issues which fundamental knowledge remains scarce. Herein, we present results regarding sputter-deposited titanium nitride oxynitride films HER. Electrochemical, fluorescence UV absorption measurements show that exhibits under acidic conditions (pH 1.6, 3.2) but is inactive at pH 7. Ti HER all these values. In contrast, TiN - with no oxygen content upon deposition both above This difference in oxynitride/nitride reactivity observed despite fact exhibit very similar surface chemical compositions predominantly TiIV oxide exposure to ambient, as determined by ex situ X-ray photoelectron spectroscopy (XPS). XPS, transfer between electrochemical UHV environments, however, demonstrates this top layer unstable conditions, stable 7, explaining inactivity pH. neutral explained DFT-based calculations showing N2 adsorption N-ligated centers energetically significantly less favorable than O-ligated centers. These also predict will not bind due a lack π-backbonding. Ex XPS probe 3.2 demonstrate undergo gradual dissolution conditions. long-term catalyst stability maintenance metal cations intermediate oxidation states pi-backbonding worthy further examination.

Язык: Английский

Tandem Electrocatalytic Nitrate Reduction to Ammonia on MBenes DOI
Guike Zhang, Xiaotian Li, Kai Chen

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(13)

Опубликована: Фев. 3, 2023

We demonstrate the great feasibility of MBenes as a new class tandem catalysts for electrocatalytic nitrate reduction to ammonia (NO3 RR). As proof concept, FeB2 is first employed model MBene catalyst NO3 RR, showing maximum NH3 -Faradaic efficiency 96.8 % with corresponding yield 25.5 mg h-1 cm-2 at -0.6 V vs. RHE. Mechanistic studies reveal that exceptional RR activity arises from catalysis mechanism, is, B sites activate NO3- form intermediates, while Fe dissociate H2 O and increase *H supply on promote intermediate hydrogenation enhance -to-NH3 conversion.

Язык: Английский

Процитировано

300
Iridium single-atom catalyst for highly efficient NO electroreduction to NH3 DOI
Kai Chen, Guohui Wang, Yali Guo

и другие.

Nano Research, Год журнала: 2023, Номер 16(7), С. 8737 - 8742

Опубликована: Март 8, 2023

Язык: Английский

Процитировано

121
p-Block Antimony Single-Atom Catalysts for Nitric Oxide Electroreduction to Ammonia DOI
Kai Chen, Ying Zhang,

Jiaqi Xiang

и другие.

ACS Energy Letters, Год журнала: 2023, Номер 8(3), С. 1281 - 1288

Опубликована: Фев. 3, 2023

Electrocatalytic NO reduction to NH3 (NORR) offers a prospective approach attain both harmful removal and efficient electrosynthesis. Main-group p-block metals are promising NORR candidates but still lack adequate exploration. Herein, Sb single atoms confined in amorphous MoO3 (Sb1/a-MoO3) designed as an catalyst, exhibiting the highest yield rate of 273.5 μmol h–1 cm–2 NO-to-NH3 Faradaic efficiency 91.7% at −0.6 V vs RHE. In situ spectroscopic characterizations theoretical computations reason that outstanding performance Sb1/a-MoO3 arises from isolated Sb1 sites, which can optimize adsorption *NO/*NHO lower reaction energy barriers simultaneously exhibit higher affinity than H2O/H species. Moreover, our strategy be extended prepare Bi1/a-MoO3, showing high property, demonstrating immense potential metal single-atom catalysts toward high-performing electrocatalysis.

Язык: Английский

Процитировано

120
Self-Tandem Electrocatalytic NO Reduction to NH3 on a W Single-Atom Catalyst DOI
Kai Chen, Jiaxin Wang, Hu Zhang

и другие.

Nano Letters, Год журнала: 2023, Номер 23(5), С. 1735 - 1742

Опубликована: Фев. 14, 2023

We design single-atom W confined in MoO3-x amorphous nanosheets (W1/MoO3-x) comprising W1-O5 motifs as a highly active and durable NORR catalyst. Theoretical operando spectroscopic investigations reveal the dual functions of to (1) facilitate activation protonation NO molecules (2) promote H2O dissociation while suppressing *H dimerization increase proton supply, eventually resulting self-tandem mechanism W1/MoO3-x greatly accelerate energetics NO-to-NH3 pathway. As result, exhibits highest NH3-Faradaic efficiency 91.2% NH3 yield rate 308.6 μmol h-1 cm-2, surpassing that most previously reported catalysts.

Язык: Английский

Процитировано

99
Tandem Electrocatalytic Nitrate Reduction to Ammonia on MBenes DOI
Guike Zhang, Xiaotian Li, Kai Chen

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(13)

Опубликована: Фев. 3, 2023

Abstract We demonstrate the great feasibility of MBenes as a new class tandem catalysts for electrocatalytic nitrate reduction to ammonia (NO 3 RR). As proof concept, FeB 2 is first employed model MBene catalyst NO RR, showing maximum NH ‐Faradaic efficiency 96.8 % with corresponding yield 25.5 mg h −1 cm −2 at −0.6 V vs. RHE. Mechanistic studies reveal that exceptional RR activity arises from catalysis mechanism, is, B sites activate − form intermediates, while Fe dissociate H O and increase *H supply on promote intermediate hydrogenation enhance ‐to‐NH conversion.

Язык: Английский

Процитировано

69
Main-group indium single-atom catalysts for electrocatalytic NO reduction to NH3 DOI
Kai Chen, Nana Zhang, Fuzhou Wang

и другие.

Journal of Materials Chemistry A, Год журнала: 2023, Номер 11(13), С. 6814 - 6819

Опубликована: Янв. 1, 2023

In single atoms confined in amorphous MoO 3 (In 1 /a-MoO ) are reported to be an efficient catalyst for NO electroreduction NH , attributed the ability of single-site inhibit hydrogen evolution and optimize NO-to-NH hydrogenation energetics.

Язык: Английский

Процитировано

58
Tailoring the coordination environment of double-atom catalysts to boost electrocatalytic nitrogen reduction: a first-principles study DOI

Jiarui Wu,

Donghai Wu, Haobo Li

и другие.

Nanoscale, Год журнала: 2023, Номер 15(39), С. 16056 - 16067

Опубликована: Янв. 1, 2023

Tailoring the coordination environment is an effective strategy to modulate electronic structure and catalytic activity of atomically dispersed transition-metal (TM) catalysts, which has been widely investigated for single-atom catalysts but received less attention emerging double-atom (DACs). Herein, based on first-principles calculations, taking commonly studied N-coordinated graphene-based DACs as references, we explored effect engineering behaviors towards electrocatalytic nitrogen reduction reaction (NRR), realized through replacing one N atom by B or O form B, O, co-coordinated DACs. We found that co-coordination could significantly strengthen N2 adsorption alter pattern TM dimer active center, greatly facilitates activation. Moreover, DACs, linear scaling relationship between binding strengths key intermediates can be attenuated. Consequently, Mn2 exhibiting ultralow limiting potential -0.27 V, climb peak volcano. In addition, experimental feasibility this DAC system was also identified. Overall, benefiting from effect, chemical performance NRR boosted. This phenomena understood adjusted center due changes its microenvironment, affects strength (pattern) pathways, leading enhanced selectivity. work highlights importance in developing other important reactions.

Язык: Английский

Процитировано

47
Electrocatalytic nitrite reduction to ammonia on an Rh single-atom catalyst DOI

Jiaqi Xiang,

Hongyan Zhao, Kai Chen

и другие.

Journal of Colloid and Interface Science, Год журнала: 2024, Номер 659, С. 432 - 438

Опубликована: Янв. 4, 2024

Язык: Английский

Процитировано

38
Electroreduction of Nitrite to Ammonia over a Cobalt Single-Atom Catalyst DOI
Hongyan Zhao,

Jiaqi Xiang,

Zeyi Sun

и другие.

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 12(7), С. 2783 - 2789

Опубликована: Фев. 2, 2024

Electrochemical nitrite-to-ammonia reduction (NO2RR) holds great promise for converting harmful NO2– into valuable NH3. Herein, we develop Co single atoms dispersed on a C3N4 substrate (Co1/C3N4) as an efficient catalyst toward the NO2RR. Experimental and theoretical investigations reveal that single-atom sites can effectively active optimize formation energy of key *NOH intermediate to promote → NH3 energetics. Remarkably, Co1/C3N4 equipped in flow cell delivers exceptional NH3–Faradaic efficiency 97.9% yield rate 1080.3 μmol h–1cm–2 at industrial-level current density 355 mA cm–2, along with long-term durability 100 h electrolysis, showing considerable potential practical electrosynthesis.

Язык: Английский

Процитировано

31
PdP2 Nanoparticles on Reduced Graphene Oxide: A Catalyst for the Electrocatalytic Reduction of Nitrate to Ammonia DOI
Guohui Wang, Ying Zhang, Kai Chen

и другие.

Inorganic Chemistry, Год журнала: 2023, Номер 62(17), С. 6570 - 6575

Опубликована: Апрель 19, 2023

Palladium phosphides are explored as efficient catalysts for the electrocatalytic reduction of nitrate to ammonia (NRA). The PdP2 nanoparticles on reduced graphene oxide exhibit maximum NH3 Faradaic efficiency 98.2% with a corresponding yield rate 7.6 mg h–1 cm–2 at −0.6 V (RHE). Theoretical calculations reveal that (011) surface can not only effectively activate and hydrogenate NO3– via NOH pathway but also retard H adsorption inhibit competitive hydrogen evolution reaction.

Язык: Английский

Процитировано

34