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

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2019 Sep 17;12(18):3009.
doi: 10.3390/ma12183009.

Influence of UiO-66(Zr) Preparation Strategies in Its Catalytic Efficiency for Desulfurization Process

Alexandre M Viana  1 , Susana O Ribeiro  1 , Baltazar de Castro  1 , Salete S Balula  2 , Luís Cunha-Silva  3
Affiliations

Influence of UiO-66(Zr) Preparation Strategies in Its Catalytic Efficiency for Desulfurization Process

Alexandre M Viana et al. Materials (Basel). .

Abstract

Porous metal-organic framework (MOF) materials UiO-66(Zr) obtained by solvothermal and microwave advanced synthesis (MWAS) procedures were characterized, and their catalytic efficiency was investigated for oxidative desulfurization (ODS) processes using a multicomponent model diesel containing benzothiophene and dibenzothiophene derivatives. The preparation parameters as the cooling time after oven use in the solvothermal procedure, and also the reaction time in the MWAS method seemed to play an important role in the catalytic performance of the UiO-66(Zr) material, as well as in its recycle capacity. The material prepared by the solvothermal procedure with a fast cooling time showed the best catalytic performance (desulfurization efficiency of 99.5% after 3 h). However, the application of the UiO-66(Zr) material prepared by the MWAS method (desulfurization efficiency of 96% after 3 h) conciliated a higher number of advantages, such as shorter reaction time preparation (15 min) and high catalytic activity for a higher number of reaction cycles. The UiO-66(Zr) prepared by the MWAS method was used for the first time in an oxidative desulfurization process, and according to the catalytic results obtained (high recycle capacity and stability) and shorter reaction time preparation, seems to be a promising material for industrial application.

Keywords: UiO-66(Zr); heterogeneous catalysis; microwave assisted synthesis; oxidative desulfurization; porous metal-organic frameworks; solvothermal synthesis.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
(a) Defect-free [Zr6O4(OH)4] cluster centre coordinated by 12 benzenedicarboxylate (bdc) ligands in the structure of Uio-66(Zr) and (b) the centre with a defect site; (c) 3D porous structure of MOF UiO-66(Zr). H-atoms were omitted for clarity proposes. Images prepared from the CIF file obtained from CDS with code RUBTAK04 and reported by Trickett and co-workers [7].
Figure 2
Figure 2
(a) powder X-ray diffraction (PXRD) patterns and (b) attenuated total reflectance operation mode (FTIR-ATR) spectra of the UiO-66(Zr) materials isolated by different synthetic methods, shown in the 2θ range 5–40° and in the wavenumber region 1800–400 cm−1, respectively.
Figure 3
Figure 3
Electron dispersive X-ray spectroscopy (EDS) spectra and SEM images for the (a) UiO-66(Zr)-S1 and (b) UiO-66(Zr)-MW2 materials.
Figure 4
Figure 4
The desulfurization profiles using a biphasic model diesel/MeCN (1:1) system and H2O2 as an oxidant (H2O2/S = 13), at 50 °C: using UiO-66(Zr) catalysts prepared by the solvothermal method UiO-66(Zr)-S1 and S2 (a) and by MWAS UiO-66(Zr)-MW1, MW2 and MWmod (b). The vertical dashed lines indicate the beginning of the catalytic step in the extractive and oxidative desulfurization (ECODS) process by adding the oxidant.
Figure 5
Figure 5
The desulfurization profile obtained the three ECODS cycles, catalyzed by UiO-66(Zr)-S1 (a) and UiO-66(Zr)-MW2 (b), using the biphasic system model diesel/MeCN (1:1) and H2O2/S=13, at 50 °C. The vertical dashed lines indicate the beginning of the catalytic step in the ECODS process by adding oxidant (H2O2).
Figure 6
Figure 6
Desulfurization efficiency of UiO-66(Zr) catalysts used in different model diesel sulfur contents under similar experimental conditions (biphasic system model diesel/MeCN system, and H2O2 as oxidant at 50–60 °C [9,37].
Figure 7
Figure 7
PXRD patterns (a) and FTIR-ATR spectra (b) of the UiO-66(Zr)-S1 and UiO-66(Zr)-MW2 materials in comparison with those after catalytic utilization [UiO-66(Zr)-S1_ac and UiO-66(Zr)-MW2_ac].
Figure 8
Figure 8
EDS spectra and SEM images of the UiO-66(Zr)-S1 (a) and UiO-66(Zr)-MW2 (b) materials in comparison with those after catalytic use [UiO-66(Zr)-S1_ac and UiO-66(Zr)-MW2_ac].
See this image and copyright information in PMC

References

    1. Fox E.B., Liu Z.-W., Liu Z.-T. Ultraclean fuels production and utilization for the twenty-first century: Advances toward sustainable transportation fuels. Energy Fuels. 2013;27:6335–6338. doi: 10.1021/ef401094t. - DOI
    1. Srivastava V.C. An evaluation of desulfurization technologies for sulfur removal from liquid fuels. RSC Adv. 2012;2:759–783. doi: 10.1039/C1RA00309G. - DOI
    1. Babich I.V., Moulijn J.A. Science and technology of novel processes for deep desulfurization of oil refinery streams: A review. Fuel. 2003;82:607–631. doi: 10.1016/S0016-2361(02)00324-1. - DOI
    1. Ibrahim M.H., Hayyan M., Hashim M.A., Hayyan A. The role of ionic liquids in desulfurization of fuels: A. review. Renew. Sustain. Energy Rev. 2017;76:1534–1549. doi: 10.1016/j.rser.2016.11.194. - DOI
    1. Campos-Martin J.M., Capel-Sanchez M.C., Perez-Presas P., Fierro J.L.G. Oxidative processes of desulfurization of liquid fuels. J. Chem. Technol. Biotechnol. 2010;85:879–890. doi: 10.1002/jctb.2371. - DOI

LinkOut - more resources