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. 2021 Nov 3;13(43):51628-51642.
doi: 10.1021/acsami.1c12126. Epub 2021 Oct 22.

Linking the Defective Structure of Boron-Doped Carbon Nano-Onions with Their Catalytic Properties: Experimental and Theoretical Studies

Grzegorz S Szymanski  1 , Yuka Suzuki  2 , Tomonori Ohba  2 , Bogdan Sulikowski  3 , Kinga Góra-Marek  4 , Karolina A Tarach  4 , Stanislaw Koter  5 , Piotr Kowalczyk  6 , Anna Ilnicka  7 , Monika Zięba  1 , Luis Echegoyen  8 , Artur P Terzyk  1 , Marta E Plonska-Brzezinska  9
Affiliations

Linking the Defective Structure of Boron-Doped Carbon Nano-Onions with Their Catalytic Properties: Experimental and Theoretical Studies

Grzegorz S Szymanski et al. ACS Appl Mater Interfaces. .

Abstract

Defects are widely present in nanomaterials, and they are recognized as the active sites that tune surface properties in the local region for catalysis. Recently, the theory linking defect structures and catalytic properties of nanocatalysts has been most commonly described. In this study, we prepared boron-doped carbon nano-onions (B-CNOs) by applying an annealing treatment of ultradispersed nanodiamond particles and amorphous boron. These experimental conditions guarantee doping of CNOs with boron atoms in the entire carbon nanostructure, thereby ensuring structural homogeneity. In our research, we discuss the correlations between defective structures of B-CNOs with their catalytic properties toward SO2 and tert-butanol dehydration. We show that there is a close relationship between the catalytic properties of the B-CNOs and the experimental conditions for their formation. It is not only the mass of the substrates used for the formation of B-CNOs that is crucial, that is, the mass ratio of NDs to amorphous B, but also the process, including temperature and gas atmosphere. As it was expected, all B-CNOs demonstrated significant catalytic activity in HSO3- oxidation. However, the subsequent annealing in an air atmosphere diminished their catalytic activity. Unfortunately, no direct relationship between the catalytic activity and the presence of heteroatoms on the B-CNO surface was observed. There was a linear dependence between catalytic activity and Raman reactivity factors for each of the B-CNO materials. In contrast to SO2 oxidation, the B-CNO-a samples showed higher catalytic activity in tert-butanol dehydration due to the presence of Brønsted and Lewis acid sites. The occurence of three types of boron-Lewis sites differing in electron donor properties was confirmed using quantitative infrared spectroscopic measurements of pyridine adsorption.

Keywords: boron; carbon nano-onion; carbon nanostructure; catalysis; defect; doping.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(A,B,D,E,G,H) HRTEM images with (C,F,I) EDS analysis of the (A) 1B-CNOs, (B,C) 1B-CNOs-a, (D) 2B-CNOs, (E,F) 2B-CNOs-a, (G) 3B-CNOs and (H,I) 3B-CNOs-a.
Figure 2
Figure 2
XPS spectra of the 1B-CNOs: (A) C 1s, (B) O 1s, (C) B 1s and (D) N 1s spectral regions.
Figure 3
Figure 3
Comparison of the 11B MAS NMR spectra of (A) 1B-CNOs; (B) 1B-CNOs-a; (C) 2B-CNOs; (D) 2B-CNOs-a; (E) 3B-CNOs, and (F) 3B-CNOs-a acquired at 160.5 MHz and a magic-angle-spinning speed of 10 kHz. The asterisks denote spinning side-bands.
Figure 4
Figure 4
Decompositions of Raman spectra of first-order (A) and second-order (B) 1B-CNOs on several spectral components (λ = 532 nm). Please see the text and Table S4 for details.
Figure 5
Figure 5
XRD patterns of B-doped CNOs.
Figure 6
Figure 6
Water adsorption isotherms (symbols) at 303 K for the studied nanomaterials. Solid line shows the fitting using eq 2 with the separated adsorption from the Langmuir (red solid line) and Dubinin–Serpinski (blue solid line) contributions.
Figure 7
Figure 7
Fourier transform IR spectra of Py adsorbed at 45 °C on the B-doped CNO materials.
Figure 8
Figure 8
(A) Catalytic activity of B-doped CNOs in SO2 oxidation. (B) Catalytic stability of 3B-CNOs in the tests of SO2 oxidation.
Figure 9
Figure 9
Catalytic activity of the studied B-CNOs in tert-butanol dehydration, (A) not annealed; and (B) annealed.
Figure 10
Figure 10
Effect of iso-butylamine (iBuNH2) dosing into the microreactor on isobutene formation during subsequent periodic injections of tert-butanol (1 μL).
See this image and copyright information in PMC

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