Saponites containing divalent transition metal cations in octahedral positions - Exploration of synthesis possibilities using microwave radiation and NMR characterization

The synthesis using microwave radiation of saponites containing Co2+, Zn2+ or Cu2+ in octahedral positions has been explored (in the case of Cu2+, together with Mg2+ or Ni2+). Pure saponite phases were formed under some synthesis conditions, although in other cases some impurities were also formed. Microwave treatment at 180 °C favored the formation of ordered solids, but induced the crystallization of other phases in some cases. Cu2+-containing saponites were formed only if Mg2+ or Ni2+ were used as octahedral sheet co-cations. The solids were characterized by different techniques, including MAS-NMR spectroscopy, which gave very precise information in the case of Zn-saponite, allowing us to estimate the content of tetrahedral Al, but much more undefined information for samples with paramagnetic cations. Nevertheless, the presence of tetrahedral Fe3+ and octahedral Fe2+ species was evidenced. Cu2+ slightly perturbed the NMR signals, while Co2+ strongly perturbed 27Al, 23Na and especially 29Si NMR spectral signals.The authors thank the financial support from the Spanish Ministry of Economy and Competitiveness (MINECO, grant MAT2013-47811-C2-R) and the European Regional Development Fund (FEDER)

Saponites containing divalent transition metal cations in octahedral positions - Exploration of synthesis possibilities using microwave radiation and NMR characterization

The synthesis using microwave radiation of saponites containing Co2+, Zn2+ or Cu2+ in octahedral positions has been explored (in the case of Cu2+, together with Mg2+ or Ni2+). Pure saponite phases were formed under some synthesis conditions, although in other cases some impurities were also formed. Microwave treatment at 180 °C favored the formation of ordered solids, but induced the crystallization of other phases in some cases. Cu2+-containing saponites were formed only if Mg2+ or Ni2+ were used as octahedral sheet co-cations. The solids were characterized by different techniques, including MAS-NMR spectroscopy, which gave very precise information in the case of Zn-saponite, allowing us to estimate the content of tetrahedral Al, but much more undefined information for samples with paramagnetic cations. Nevertheless, the presence of tetrahedral Fe3+ and octahedral Fe2+ species was evidenced. Cu2+ slightly perturbed the NMR signals, while Co2+ strongly perturbed 27Al, 23Na and especially 29Si NMR spectral signals.The authors thank the financial support from the Spanish Ministry of Economy and Competitiveness (MINECO, grant MAT2013-47811-C2-R) and the European Regional Development Fund (FEDER)