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1. Enhanced CO ₂ electrolysis with a SrTiO ₃ cathode through a dual doping strategy

   https://doi.org/10.1039/c8ta10188d  

   Ye, Lingting; Hu, Xiuli; Wang, Xin; Chen, Fanglin; Tang, Dian; Dong, Dehua; Xie, Kui (February 2019, Journal of Materials Chemistry A)

   The significant role of perovskite defect chemistry through A-site doping of strontium titanate with lanthanum for CO 2 electrolysis properties is demonstrated. Here we present a dual strategy of A-site deficiency and promoting adsorption/activation by making use of redox active dopants such as Mn/Cr linked to oxygen vacancies to facilitate CO 2 reduction at perovskite titanate cathode surfaces. Solid oxide electrolysers based on oxygen-excess La 0.2 Sr 0.8 Ti 0.9 Mn(Cr) 0.1 O 3+δ , A-site deficient (La 0.2 Sr 0.8 ) 0.9 Ti 0.9 Mn(Cr) 0.1 O 3−δ and undoped La 0.2 Sr 0.8 Ti 1.0 O 3+δ cathodes are evaluated. In situ infrared spectroscopy reveals that the adsorbed and activated CO 2 adopts an intermediate chemical state between a carbon dioxide molecule and a carbonate ion. The double strategy leads to optimal performance being observed after 100 h of high-temperature operation and 3 redox cycles, suggesting a promising cathode material for CO 2 electrolysis. 

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2. Stabilizing the B-site oxidation state in ABO ₃ perovskite nanoparticles

   https://doi.org/10.1039/C9NR04155A  

   Ofoegbuna, Tochukwu; Darapaneni, Pragathi; Sahu, Smriti; Plaisance, Craig; Dorman, James A. (August 2019, Nanoscale)

   The stabilization of the B-site oxidation state in ABO 3 perovskites using wet-chemical methods is a synthetic challenge, which is of fundamental and practical interest for energy storage and conversion devices. In this work, defect-controlled (Sr-deficiency and oxygen vacancies) strontium niobium( iv ) oxide (Sr 1−x NbO 3−δ , SNO) metal oxide nanoparticles (NPs) were synthesized for the first time using a low-pressure wet-chemistry synthesis. The experiments were performed under reduced oxygen partial pressure to prevent by-product formation and with varying Sr/Nb molar ratio to favor the formation of Nb 4+ pervoskites. At a critical Sr to Nb ratio (Sr/Nb = 1.3), a phase transition is observed forming an oxygen-deficient SrNbO 3 phase. Structural refinement on the resultant diffraction pattern shows that the SNO NPs consists of a near equal mixture of SrNbO 3 and Sr 0.7 NbO 3−δ crystal phases. A combination of Rietveld refinement and X-ray photoelectron spectroscopy (XPS) confirmed the stabilization of the +4 oxidation state and the formation of oxygen vacancies. The Nb local site symmetry was extracted through Raman spectroscopy and modeled using DFT. As further confirmation, the particles demonstrate the expected absorption highlighting their restored optoelectronic properties. This low-pressure wet-chemical approach for stabilizing the oxidation state of a transition metal has the potential to be extended to other oxygen sensitive, low dimensional perovskite oxides with unique properties. 

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3. Tuning Nb Solubility, Electrical Properties, and Imprint through PbO Stoichiometry in PZT Films

   https://doi.org/10.3390/ma16113970  

   Akkopru-Akgun, Betul; Trolier-McKinstry, Susan (June 2023, Materials)

   Lead zirconate titanate (PZT) films with high Nb concentrations (6–13 mol%) were grown by chemical solution deposition. In concentrations up to 8 mol% Nb, the films self-compensate the stoichiometry; single phase films were grown from precursor solutions with 10 mol% PbO excess. Higher Nb concentrations induced multi-phase films unless the amount of excess PbO in the precursor solution was reduced. Phase pure perovskite films were grown with 13 mol% excess Nb with the addition of 6 mol% PbO. Charge compensation was achieved by creating lead vacancies when decreasing excess PbO level; using Kroger-Vink notation, NbTi• are ionically compensated by VPb″ to maintain charge neutrality in heavily Nb-doped PZT films. With Nb doping, films showed suppressed {100} orientation, the Curie temperature decreased, and the maximum in the relative permittivity at the phase transition broadened. The dielectric and piezoelectric properties were dramatically degraded due to increased quantity of the non-polar pyrochlore phase in multi-phase films; εr reduced from 1360 ± 8 to 940 ± 6, and the remanent d33,f value decreased from 112 to 42 pm/V when increasing the Nb concentration from 6 to 13 mol%. Property deterioration was corrected by decreasing the PbO level to 6 mol%; phase pure perovskite films were attained. εr and the remanent d33,f increased to 1330 ± 9 and 106 ± 4 pm/V, respectively. There was no discernable difference in the level of self-imprint in phase pure PZT films with Nb doping. However, the magnitude of the internal field after thermal poling at 150 °C increased significantly; the level of imprint was 30 kV/cm and 11.5 kV/cm in phase pure 6 mol% and 13 mol% Nb-doped films, respectively. The absence of mobile VO••, coupled with the immobile VPb″ in 13 mol% Nb-doped PZT films, leads to lower internal field formation upon thermal poling. For 6 mol% Nb-doped PZT films, the internal field formation was primarily governed by (1) the alignment of (VPb″−VO•• )x and (2) the injection and subsequent electron trapping by Ti4+. For 13 mol% Nb-doped PZT films, hole migration between VPb″ controlled internal field formation upon thermal poling. 

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4. Titanite zonation records magmatic to autometamorphic transition in the Little Cottonwood stock, Utah

   Bartley, J.M.; Stearns, M.A.; Bowman, J.R.; Beno, C.J.; Saunders, E.; Nicholas, S. (April 2023, Abstracts Geological Society of America)

   Granite textures are usually assumed to be unmodified igneous features, but titanite petrochronoloy records a progression from magmatic crystallization to fluid-mediated automorphism in the Little Cottonwood stock (LCS). The Wasatch Mountains expose a profile through the 36-25 Ma Wasatch Igneous Belt owing to 20° eastward tilt in the footwall of the Wasatch Fault. The LCS, Alta stock (AS) and their contact aureoles form an integrated magmatic-hydrothermal system that underpinned the cogenetic Keetley Volcanics (KV). The AS (~3-5 km depth) likely formed a conduit from the deeper LCS (~6-11 km) to the KV. The LCS formed in two phases: 1) ~36–33 Ma, coeval with the AS and KV, and 2) ~32–25 Ma, younger than KV and AS but at this time hydrothermal fluid infiltrated the AS­ to form endoskarn. LCS titanite was analyzed by LASS-ICP-MS in 16 samples of unaltered granite (s.l.) collected along transects from the roof on the east to the deepest exposures on the west and from the northern wall to the southern wall. Principal component analysis of titanite trace-element data distinguishes a magmatic group with high REE and a metamorphic group with low REE and high W, Sr, Sc, V, Cr, Fe, Al, and Pb. The metamorphic group forms BSE-dark rims that are variably developed but present in every sample. U-Pb dates indicate that, across the sample suite, there is nearly complete age overlap between magmatic and metamorphic titanite. We interpret chemical zoning of the titanite to record magmatic crystallization followed by hydrothermal modification of primary minerals. The age overlap suggests that solidified increments were infiltrated by fluid released by crystallization of nearby later increments. Infiltrating fluids also affected the feldspars: although apparently intact when examined optically, CL images reveal the feldspars to have been shattered, then healed by dissolution-reprecipitation. Exsolution of Ab component from K-feldspar to form albite selvages against adjacent plagioclase probably was part of the same process, as were biotite chloritization and exsolution of Ti from primary titanomagnetite to grow metamorphic titanite. Taken together, observations from titanite and major phases are consistent with fluid-mediated submagmatic re-equilibration throughout incremental assembly of the LCS. 

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5. Trace and Rare Earth Element Compositions of Lawsonite as a Chemical Tracer of Metamorphic Processes in Subduction Zones

   https://doi.org/10.1093/petrology/egac065  

   Kang, Patricia; Whitney, Donna L; Martin, Laure A; Fornash, Katherine F (August 2022, Journal of Petrology)

   Abstract Lawsonite is a major host mineral of trace elements (TEs; e.g. REE, Sr, Pb, U, Th) and H2O in various rock types (metabasite, metasediment, metasomatite) over a wide range of depths in subduction zones. Consequently, the composition of lawsonite is a useful archive to track chemical exchanges that occurred during subduction and/or exhumation, as recorded in high-pressure/low-temperature (HP/LT) terranes. This study provides an extensive dataset of major element and TE compositions of lawsonite in HP/LT rocks from two mélanges (Franciscan/USA; Rio San Juan/Dominican Republic), two structurally coherent terranes (Tavşanlı/Turkey; Alpine Corsica/France), and the eclogite blocks of the Pinchi Lake/Canada complex. Bulk major and TE compositions were also determined for lawsonite-bearing host rocks to understand petrogenesis and assess compositional evolution. Most analyzed mélange and coherent-terrane metabasalts have normal mid-ocean ridge/back-arc basin basalt signatures and they preserve compositional evidence supporting interactions with (meta)sediment ± metagabbro/serpentinite (e.g. LILE/LREE enrichments; Ni/Cr enrichments). Most lawsonite grains analyzed are compositionally zoned in transition-metal elements (Fe, Ti, Cr), other TEs (e.g. Sr, Pb), and/or REE, with some grains showing compositional variations that correlate with zoning patterns (e.g. Ti-sector zoning, core-to-rim zoning in Fe, Cr-oscillatory zoning). Our results suggest that compositional variations in lawsonite formed in response to crystallographic control (in Ti-sector zoning), fluid–host rock interactions, modal changes in minerals, and/or element fractionation with coexisting minerals that compete for TEs (e.g. epidote, titanite). The Cr/V and Sr/Pb ratios of lawsonite are useful to track the compositional influence of serpentinite/metagabbro (high Cr/V) and quartz-rich (meta)sediment (low Sr/Pb). Therefore, lawsonite trace and rare earth element compositions effectively record element redistribution driven by metamorphic reactions and fluid–rock interactions that occurred in subduction systems. 

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