Probing the interaction of U(vi) with phosphonate-functionalized mesoporous silica using solid-state NMR spectroscopy.
The fundamental interaction of U(vi) with diethylphosphatoethyl triethoxysilane functionalized SBA-15 mesoporous silica is studied by macroscopic batch experiments and solid-state NMR spectroscopy. DPTS-functionalized silica has been shown to extract U(vi) from nitric acid solutions at or above pH 3. Extraction is dependent on pH and ionic strength. Single-pulse (31)P NMR on U(vi) contacted samples revealed that U(vi) only interacts with a fraction of the ligands present on the surface. At pH 4 the U(vi) extraction capacity of the material is limited to 27-37% of the theoretical capacity, based on ligand loading. We combined single pulse (31)P NMR on U(vi)-contacted samples with batch studies to measure a ligand-to-metal ratio of approximately 2 : 1 at pH 3 and 4. Batch studies and cross-polarization NMR measurements reveal that U(vi) binds to deprotonated phosphonate and/or silanol sites. We use (31)P-(31)P DQ-DRENAR NMR studies to compare the average dipolar coupling between phosphorus spins for both U(vi)-complexed and non-complexed ligand environments. These measurements reveal that U(vi) extraction is not limited by inadequate surface distribution of ligands, but rather by low stability of the surface phosphonate complex.
Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, USA. eva.uribe@berkeley.edu.
Eva C
EC
Uribe
Glenn T. Seaborg Institute, Physical and Life Sciences Directorate, Lawrence Livermore National Laboratory, L-231, PO Box 808, Livermore, California 94550, USA.
Harris E
HE
Mason
Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, USA. eva.uribe@berkeley.edu and Glenn T. Seaborg Institute, Physical and Life Sciences Directorate, Lawrence Livermore National Laboratory, L-231, PO Box 808, Livermore, California 94550, USA.
Jennifer A
JA
Shusterman
Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, USA. eva.uribe@berkeley.edu.
Anthony
A
Bruchet
Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, USA. eva.uribe@berkeley.edu.
Heino
H
Nitsche