RT Journal Article
T1 Structural characterization, proton conductivity and furfural catalysis of novel polyfunctional zirconium phosphonates
A1 Bazaga-García, Montse
A1 Pérez-Colodrero, Rosario Mercedes
A1 Vílchez-Cózar, Álvaro
A1 Olivera-Pastor, Pascual
A1 Cecilia-Buenestado, Juan Antonio
A1 Kurowski, Łukasz
A1 Zaręba, Jan K.
A1 Cabeza-Díaz, Aurelio
K1 Química inorgánica
K1 Circonio
K1 Catálisis
AB Zirconium phosphonates combine the thermal robustness of Zr–O frameworks with the rich functionality of organophosphonic linkers, making them attractive for both energy-related and catalytic applications. Here, we report three new crystalline Zr(IV) phosphonates built from 5-(dihydroxyphosphoryl)-isophthalic acid (PiPhtA), 5-(dihydroxyphosphoryl)-nicotinic acid (PNA) and benzene-1,2,3-triyltris(methylenephosphonic acid) (BTTMPA). Phase-pure Zr[(HO3P-C6H3-(COOH)2)2(X)2]·6H2O (X = F−/OH−) (Zr-PiPhtA), Zr(O3P-NH+-C5H3-COOH)2F2 (Zr-PNA) and Zr[(H2O3PCH2)(O3PCH2)2-C6H3]·H2O (Zr-BTTMP) were obtained under mild solvothermal conditions and characterized by synchrotron powderX-ray diffraction, pair distribution function (PDF) analysis, solid-state NMR and thermogravimetry. The crystal structures of 1D Zr-PNA (P21/c) and 3D Zr-BTTMP (P21/a) were solved ab initio from powder diffraction data, while combined structural X-ray diffraction and PDF analyses together with ammonia adsorption suggest that nanocrystalline Zr-PiPhtA exhibits features resembling those of the analogous Ca-PiPhtA derivative and Zr-BTTMP. Given that all of them exhibit characteristics adequate for facilitating proton transfer pathways, a study of proton conductivity was undertaken. Under 95% relative humidity, bulk proton conductivities reach 1.2 × 10−3 S cm−1 (Zr-BTTMP) at 80 °C. On exposure to NH3 vapour, theconductivity of Zr-PiPhtA and Zr-PNA increased by almost one order of magnitude, up to 3.2 × 10−3 S cm−1 at 80 °C for Zr-PiPhtA, highlighting the decisive role of ammonium-assisted proton hopping. The same acid sites that promote proton mobility also endow the materials with bifunctional catalytic behavior. In the one-pot cascade upgrading of furfural, Zr-PiPhtA afforded the highest overall conversions, benefiting from the nanocrystalline morphology and a higher density of strong Brønsted acid sites.
PB Royal Society of Chemistry
SN 5667-5678
YR 2026
FD 2026
LK https://hdl.handle.net/10630/46542
UL https://hdl.handle.net/10630/46542
LA eng
NO Bazaga-García, M., Colodrero, R. M. P., Vílchez-Cózar, Á., Olivera-Pastor, P., Cecilia, J. A., Kurowski, Ł., Zaręba, J. K., & Cabeza, A. (2026). Structural characterization, proton conductivity and furfural catalysis of novel polyfunctional zirconium phosphonates. Dalton Trans., 55(14), 5667-5678. https://doi.org/10.1039/D5DT02947C
NO Funding for open access charge: Universidad de Málaga/CBUA.
NO Ministerio de Ciencia, Innovación y Universidades
NO European Union
NO Junta de Andalucía
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 26 may 2026