Influence of iron content in palladium catalysts supported on alumina and their reduction conditions on the hydrodechlorination of diclofenac in aqueous solutions

E. S. Lokteva; Локтева Е. С.; M. D. Pesotskiy; Песоцкий М. Д.; E. V. Golubina; Голубина Е. В.; K. I. Maslako; Маслаков К. И.; A. N. Kharlanov; Харланов А. Н.; V. V. Shishova; Шишова В. В.; I. Yu. Kaplin; Каплин И. Ю.; S. V. Maksimov; Максимов С. В.

doi:10.31857/S0453881124020054

Influence of iron content in palladium catalysts supported on alumina and their reduction conditions on the hydrodechlorination of diclofenac in aqueous solutions

Authors: Lokteva E.S.¹, Pesotskiy M.D.¹, Golubina E.V.¹, Maslako K.I.¹, Kharlanov A.N.¹, Shishova V.V.¹, Kaplin I.Y.¹, Maksimov S.V.¹
Affiliations:
1. Lomonosov Moscow State University
Issue: Vol 65, No 2 (2024)
Pages: 148-172
Section: ARTICLES
URL: https://journal-vniispk.ru/0453-8811/article/view/265003
DOI: https://doi.org/10.31857/S0453881124020054
EDN: https://elibrary.ru/DWUAEN
ID: 265003

Cite item

Full Text

Open Access
Restricted Access

Access granted
Restricted Access

Subscription Access

Abstract
Full Text
About the authors
References
Supplementary files
Statistics

Abstract

Using the method of wet impregnation of alumina with iron and palladium nitrates, 1Pd0.5Fe and 1Pd10Fe catalysts modified with iron oxides were prepared with a target content of 1 wt % Pd, 0.5 or 10 wt % iron. The catalysts were compared with each other and with the monometallic catalyst 1Pd in the hydrodechlorination (HDC) of diclofenac (DCF) in dilute aqueous solutions at 30°C in batch and flow reactors after high-temperature (320°C) and mild (30°C) reduction; the latter was carried out in a batch or flow reactor. Using X-ray photoelectron spectroscopy (XPS), it was shown that after reduction at 320°C the surface of catalysts contains mainly Pd⁰, Fe²⁺ and Fe³⁺. The surface Fe²⁺/Fe³⁺ ratio increases as the iron content decreases. The reduction of Pd²⁺ to Pd⁰ is possible already at 30°C, but it proceeds much worse on the surface of 1Pd0.5Fe compared to 1Pd10Fe. According to XPS data, temperature-programmed reduction and infrared spectroscopy of diffuse reflection of adsorbed CO, modification with iron oxides increases the palladium content on the surface compared to 1Pd, promotes the emergence of new Pd–O–Fe centers, and affects the ability of palladium to be reduced. These effects increase with increasing iron content. Iron-modified catalysts reduced at 320°C showed similar activity and stability in the conversion of DCP in flow-through and batch systems. Unlike 1Pd0.5Fe, the 1Pd10Fe catalyst is highly efficient and stable even after mild reduction at 30°C. Under flow conditions with comparable DCF conversion, it provides increased selectivity in the HDC reaction of diclofenac compared to 1Pd, which is also active in hydrogenation.

Keywords

hydrodechlorination, diclofenac, palladium, iron oxide, aluminum oxide, environmental catalysis

Full Text

Russian Federation, Leninskie Gory, 1, building 3, Moscow, 119991

References

Xu S., Zhou S., Xing L., Shi P., Shi W., Zhou Q., Pan Y., Song M.-Y., Li A. // Sci. Total Environ. 2019. V. 682. P. 756.
Zhao J., Wang Q., Fu Y., Peng B., Zhou G. // Environ. Sci. Pollut. Res. 2018. V. 25. P. 22998.
Umbreen N., Sohni S., Ahmad I., Khattak N.U., Gul K. // J. Colloid Interface Sci. 2018. V. 527. P. 356.
Gros M., Petrović M., Barceló D. // Environ. Tox. Chem. 2007. V. 26. P. 1553.
Dobrin D., Bradu C., Magureanu M., Mandache N.B., Pârvulescu V.I. // Chem. Eng. J. 2013. V. 234. P. 389.
Lokteva E., Golubina E., Likholobov V., Lunin V., Disposal of Chlorine-Containing Wastes / In: Chemistry Beyond Chlorine, Springer International Publishing. Eds. P. Tundo, L.-N. He, E. Lokteva and C. Mota, Cham, 2016. 559 p. https://doi.org/10.1007/978-3-319-30073-3_21
Munoz M., Mora F.J., de Pedro Z.M., Alvarez-Torrellas S., Casas J.A., Rodriguez J.J. // J. Hazard. Mater. 2017. V. 331. P. 45.
Nieto-Sandoval J., Munoz M., de Pedro Z.M., Casas J.A. // J. Hazard. Mater. Adv. 2022. V. 5. P. 100047.
Lokteva E.S., Shishova V.V., Maslakov K.I., Golubina E.V., Kharlanov A.N., Rodin I.A., Vokuev M.F., Filimonov D.S., Tolkachev N.N. // Appl. Surf. Sci. 2023. V. 613. P. 156022.
Wu K., Qian X., Chen L., Xu Z., Zheng S., Zhu D. // RSC Adv. 2015. V. 5. P. 18702.
Nieto-Sandoval J., Munoz M., de Pedro Z.M., Casas J.A. // Chemosphere. 2018. V. 213. P. 141.
Zhou T., Li Y., Lim T.-T. // Separ. Purif. Technol. 2010. V. 76. P. 206.
Liu M., Huang R., Li C., Che M., Su R., Li S., Yu J., Qi W., He Z. // Chem. Eng. Sci. 2019. V. 201. P. 121.
Witońska I.A., Walock M.J., Binczarski M., Lesiak M., Stanishevsky A.V., Karski S. // J. Mol. Catal. A: Chem. 2014. V. 393. P. 248.
Zhang L., Meng Z., Zang S. // J. Environ. Sci. 2015. V. 31. P. 194.
Lokteva E.S., Shishova V.V., Tolkachev N.N., Maslakov K.I., Kamaev A.O., Maksimov S.V., Golubina E.V. // Mendeleev Commun. 2022. V. 32. P. 249.
Silva J.M., Araújo J.F.D.F., Brocchi E., Solórzano I.G. // Ceram. Int. 2020. V. 46. P. 19052.
Th P., Zimmermann R., Steiner P., Hüfner S. // J. Phys. Condens. Matter. 1997. V. 9. P. 3987.
Amoyal M., Vidruk-Nehemya R., Landau M.V., Herskowitz M. // J. Catal. 2017. V. 348. P. 29.
Armenta M.A., Maytorena V.M., Flores-Sánchez L.A., Quintana J.M., Valdez R., Olivas A. // Fuel. 2020. V. 280. P. 118545.
Tian Z., Zhang W., Liu T., Liu J., Wang C., Lei L., Liao M., Wang C., Chen Y. // Int. J. Hydrogen Energy. 2022. V. 47. P. 41468.
Han X., Qing M., Wang H., Yu X., Suo H.-Y., Shen X.-F., Yang Y., Li Y.-W. // J. Fuel Chem. Technol. 2023. V. 51. P. 155.
Lu Z.-Y., Muir D.M. // Hydrometallurgy. 1988. V. 21. P. 9.
Tao F., Dag S., Wang L.-W., Liu Z., Butcher D.R., Bluhm H., Salmeron M., Somorjai G.A. // Science. 2010. V. 327. P. 850.
Boudart M., Hwang H.S. // J. Catal. 1975. V. 39. P. 44.
Babu N.S., Lingaiah N., Kumar J.V., Prasad P.S.S. // Appl. Catal. A: Gen. 2009. V. 367. P. 70.
Lieltz G., Nimz M., Völter J., Läzär K., Guczi L. // Appl. Catal. 1988. V. 45. P. 71.
Berry F.J., Changhai X., Jobson S. // J. Chem. Soc. Faraday Trans. 1990. V. 86. P. 165.
Arnoldy P., Moulijn J.A. // J. Catal. 1985. V. 93. P. 38.
Arnoldy P., van Oers E.M., Bruinsma O.S.L., de Beer V.H.J., Moulijn J.A. // J. Catal. 1985. V. 93. P. 231.
Sepúlveda J.H., Fígoli N.S. // Appl. Surf. Sci. 1993. V. 68. P. 257.
Pino N., Sitthisa S., Tan Q., Souza T., López D., Resasco D.E. // J. Catal. 2017. V. 350. P. 30.
Liu W., Ismail M., Dunstan M.T., Hu W., Zhang Z., Fennell P.S., Scott S.A., Dennis J.S. // RSC Adv. 2015. V. 5. P. 1759.
Tataroğlu A., Al-Ghamdi A.A., El-Tantawy F., Farooq W.A., Yakuphanoğlu F. // Appl. Phys. A. 2016. V. 122. P. 220.
Jastrzębska I., Szczerba J., Błachowski A., Stoch P. // Eur. J. Mineral. 2017. V. 29. P. 62.
Yewale A.D., Kherdekar P.V., Bhatia D. // Chem. Eng. Sci. 2022. V. 249. P. 117281.
Kamada T., Ueda T., Fukuura S., Yumura T., Hosokawa S., Tanaka T., Kan D., Shimakawa Y. // J. Am. Chem. Soc. 2023. V. 145. P. 1631.
Schwertmann U. // Plant and Soil. 1991. V. 130. P. 1.
Sidhu P.S., Gilkes R.J., Cornell R.M., Posner A.M., Quirk J.P. // Clays and Clay Minerals. 1981. V. 29. P. 269
Kolev N.I. Solubility of O2, N2, H2 and CO2 in water / In: Multiphase Flow Dynamics 4: Turbulence, Gas Adsorption and Release, Diesel Fuel Properties. Ed. N.I. Kolev. Berlin, Heidelberg: Springer, 2012.209 р. https://doi.org/10.1007/978-3-642-20749-5_11

Supplementary files

Supplementary Files

Action

1. JATS XML

Download

2. Scheme 1. Diclofenac HDC scheme.

Download (198KB)

Indexing metadata

3. Fig. 1. HDC of diclofenac in a batch reactor in the presence of 1Pd0.5Fe. The dotted line shows the data for 1Pd0.5Fe(30), the solid line – for 1Pd0.5Fe(320).

Download (190KB)

Indexing metadata

4. Fig. 2. HDC of DKF at 30°C in an aqueous medium in a batch reactor in the presence of palladium-iron catalysts on aluminum oxide, unreduced (no) and after preliminary reduction, the temperature of which is indicated in brackets. CO(DKF) – 150 mg/l, H2 feed rate – 0.6 l/h.

Download (167KB)

Indexing metadata

5. Fig. 3. HDC of DKF at 30°C in an aqueous medium in a flow reactor in the presence of catalysts on aluminum oxide: a – reduced at 320°C, b – reduced at 30°C directly in the reactor. Reaction conditions: C0(DKF) = 75 mg/l, mixture feed rate – 42 ml/h, H2 – 0.6 l/h, catalyst loading – 0.1 g.

Download (308KB)

Indexing metadata

6. Fig. 4. Diffraction patterns of unreduced samples.

Download (655KB)

Indexing metadata

7. Fig. 5. SEM image of the 1Pd0.5Fe catalyst (a) and distribution maps of Pd (b) and Fe (c) obtained by the EDA method.

Download (725KB)

Indexing metadata

8. Fig. 6. TEM micrographs of the 1Pd0.5Fe catalyst in bright (a) and dark (b, c, e) fields, maps of the distribution of palladium (g) and iron (e) on the surface, EDA results (h) in the 007 region shown in the image (g).

Download (1MB)

Indexing metadata

9. Fig. 7. High-resolution XPS spectra: Pd3d (a) and Fe2p (b) before and after catalyst reduction; Pd3d (c) and Cl2p (d) of 1Pd(30f) and 1Pd10Fe(30f) catalysts after catalytic testing in a flow system.

Download (1003KB)

Indexing metadata

10. Fig. 8. IR DO spectra of CO adsorbed on catalysts at room temperature and a CO pressure of 50 Torr, after heat treatment in vacuum at 550°C and subsequent reductive treatment with H2 at 320°C for 1 h. F(R) is the Kubelka–Munk function. The intensity of the 1Pd10Fe(320) spectrum is reduced by 3 times.

Download (237KB)

Indexing metadata

11. Fig. 9. TPV profiles of bimetallic (1Pd10Fe and 1Pd0.5Fe) and monometallic (1Pd and 10Fe) catalysts.

Download (296KB)

Indexing metadata

12. Fig. 10. Surface structure of palladium-containing catalysts after mild and high-temperature reduction.

Download (404KB)

Indexing metadata

Username
Password
Remember me

Forgot password?	Register

Username
Password
Remember me

Forgot password?	Register