Movatterモバイル変換

[0]ホーム
URL:

Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
Thehttps:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

NIH NLM Logo
Log inShow account info
Access keysNCBI HomepageMyNCBI HomepageMain ContentMain Navigation
pubmed logo
Advanced Clipboard
User Guide

Full text links

Nature Publishing Group full text link Nature Publishing Group Free PMC article
Full text links

Actions

Share

.2024 Feb 20;15(1):1535.
doi: 10.1038/s41467-024-45832-9.

Efficient catalyst-free N2 fixation by water radical cations under ambient conditions

Affiliations

Efficient catalyst-free N2 fixation by water radical cations under ambient conditions

Xiaoping Zhang et al. Nat Commun..

Abstract

The growth and sustainable development of humanity is heavily dependent upon molecular nitrogen (N2) fixation. Herein we discover ambient catalyst-free disproportionation of N2 by water plasma which occurs via the distinctive HONH-HNOH+• intermediate to yield economically valuable nitroxyl (HNO) and hydroxylamine (NH2OH) products. Calculations suggest that the reaction is prompted by the coordination of electronically excited N2 with water dimer radical cation, (H2O)2+•, in its two-center-three-electron configuration. The reaction products are collected in a 76-needle array discharge reactor with product yields of 1.14 μg cm-2 h-1 for NH2OH and 0.37 μg cm-2 h-1 for HNO. Potential applications of these compounds are demonstrated to make ammonia (for NH2OH), as well as to chemically react and convert cysteine, and serve as a neuroprotective agent (for HNO). The conversion of N2 into HNO and NH2OH by water plasma could offer great profitability and reduction of polluting emissions, thus giving an entirely look and perspectives to the problem of green N2 fixation.

© 2024. The Author(s).

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing interests.

Figures

Fig. 1
Fig. 1. Disproportionation reaction of N2 with water dimer radical cation.
a Experimental setup to study the interaction of N2 with water vapor plasma at ambient conditions. Stainless-steel discharge needle was used as electrode. DC: direct current. The figure is adapted with permission from refs.,,.b The corresponding mass spectrum of ionic products in Fig. 1a. Asterisks correspond to the products specific to the reaction between water vapor plasma and N2.c Ion trap reactor applied to study the reaction between N2 and isolated (H2O)2+• (m/z 36) in vacuum. The figure is adapted with permission from refs.,,.d The corresponding mass spectrum of ionic products inc. Asterisks correspond to the products specific to the reaction between water vapor plasma and N2.e Ionic fragments of the reaction intermediate atm/z 64 induced by collisional activation inside the ion trap.f Mass spectrum of the ionic species observed during the interaction between water vapor plasma and15N2 (15N2 gas instead of14N2 ina). Asterisks correspond to the products specific to the reaction between water vapor plasma and15N2.
Fig. 2
Fig. 2. Mechanism and calculation results for the reaction of N2 with (H2O)2+•.
a Schematic diagram summarizing a possible mechanism for the reaction of N2 with (H2O)2+•.b The geometries and energies (in eV at 298 K and 1 atm pressure) of possible molecular and ionic species involved in the disproportionation reaction N2 + (H2O)2+• → NH2OH+• + HNO calculated with CCSD(T) method. Our expected accuracy is 0.04 eV, with the exception of transition state (TS) structure (gray, see Supplementary Note 1). Vertical arrows correspond to the process of electronic excitation/de-excitation. a: [H2O•••OH2]+. p1: NH2OH+•. p2: HNO. The atomic coordinates of the optimized computational models are shown in Supplementary Data File.
Fig. 3
Fig. 3. Products of ambient disproportionation reaction of N2 with (H2O)2+• characterized by spectral methods.
a Schematic illustration of the reaction assembly for scale-up reaction and the collection of reaction products. DC: direct current. The 76 anodes of the array were connected to the same positive terminal of the DC high voltage power. The figure is adapted with permission from refs.,,.b Ultraviolet-visible spectra of indooxine formed through the online reaction of the collected NH2OH with 8-quinolinol probe at different times of the reaction between N2 and (H2O)2+•.c Infrared spectra of the collected sample (red) and NH2OH•HCl standard (black).d Raman spectra of the collected sample (red) and NH2OH•HCl standard (black).e Fluorescence spectra of 7-hydroxycoumarin formed through the online reaction of the collected HNO with P-CM probe at different times of the reaction between N2 and (H2O)2+•.f Mass spectra of P-CM solution before and after collection of the reaction mixture, showing the formation of P-CM aza-ylide (P-CM-NH) and P-CM oxide (P-CM-O) due to the reaction between P-CM and HNO. The inset figure shows the tandem mass spectrum of protonated P-CM atm/z 451. P-CM: coumarin-based fluorescent probe.
Fig. 4
Fig. 4. Further validation and application of the NH2OH and HNO products of N2 disproportionation with (H2O)2+•.
a Electrolytic reduction of the collected NH2OH product (corresponding signal atm/z 34) into NH3 (corresponding signal atm/z 35) confirmed by mass spectrometry detection. The signals atm/z 36 andm/z 37 correspond to (H2O)2+• and H+(H2O)2.b The kinetics of electrolytic reduction of NH2OH collected at different discharge voltages into NH3 determined using the indophenol blue method (see Supplementary Fig. 9).c The conversion of cysteine (corresponding signal atm/z 122) into cystine (corresponding signal atm/z 241) via the reaction of cysteine with the collected HNO product of the disproportionation reaction of N2 confirmed by mass spectrometry detection.d The kinetics of cysteine conversion into cystine via the reaction with the collected HNO product (~25 μM; collection time 30 min) at different cysteine concentrations.e Effects of different concentration levels of HNO alone on HT22 cell reducing capacity.f HT22 cells were pretreated with different concentration levels of HNO for 24 h and incubated with or without H2O2 (200 μM) for 1 h. Cell reducing capacity as determined with Cell Counting Kit-8 assay.*P < 0.05 and**P < 0.01versus control,#P < 0.05 and##P < 0.01 versus model. The error bars indicate the standard deviation (n = 3).
See this image and copyright information in PMC

Similar articles

See all similar articles

Cited by

References

    1. Yeung LY, et al. Extreme enrichment in atmospheric 15N15N. Sci. Adv. 2017;3:6741. doi: 10.1126/sciadv.aao6741. - DOI - PMC - PubMed
    1. Legare MA, et al. Nitrogen fixation and reduction at boron. Science. 2018;359:896–899. doi: 10.1126/science.aaq1684. - DOI - PubMed
    1. Hoffman BM, Lukoyanov D, Yang Z-Y, Dean DR, Seefeldt LC. Mechanism of nitrogen fixation by nitrogenase: the next stage. Chem. Rev. 2014;114:4041–4062. doi: 10.1021/cr400641x. - DOI - PMC - PubMed
    1. Chen JG, et al. Beyond fossil fuel–driven nitrogen transformations. Science. 2018;360:aar6611. doi: 10.1126/science.aar6611. - DOI - PMC - PubMed
    1. Tanabe Y, Nishibayashi Y. Comprehensive insights into synthetic nitrogen fixation assisted by molecular catalysts under ambient or mild conditions. Chem. Soc. Rev. 2021;50:5201–5242. doi: 10.1039/D0CS01341B. - DOI - PubMed

Related information

Grants and funding

LinkOut - more resources

Full text links
Nature Publishing Group full text link Nature Publishing Group Free PMC article
Cite
Send To

NCBI Literature Resources

MeSHPMCBookshelfDisclaimer

The PubMed wordmark and PubMed logo are registered trademarks of the U.S. Department of Health and Human Services (HHS). Unauthorized use of these marks is strictly prohibited.

[8]ページ先頭
©2009-2025 Movatter.jp