Sta 449 f3 jupiter thermal analyzer

The thermal analysis of the M0-M4 materials was conducted on an STA 449 F3 Jupiter thermal analyzer (Netzsch, Selb, Germany). The thermogravimetric (TG) and derivative thermogravimetric (DTG) curves of small amounts of material (10–15 mg) taken from each injection molded material and placed in 85 µL alumina (Al₂O₃) crucibles without lids were recorded in static air in the temperature range of 20–700 °C with a heating rate of 10 K/min.

The solid-state UV-Vis absorption and luminescence spectra of Th-SINAP-100 were collected on a Craic Technologies microspectrophotometer. The electron paramagnetic resonance data were recorded on a JEOL-FA200 spectrometer at the X-band with 100 kHz field modulation at room temperature. The Fourier transform infrared spectroscopy study was carried out a Thermo Nicolet 6700 spectrometer equipped with a diamond attenuated total reflectance (ATR) accessory. Elemental analyses of C, H, and N were performed on Th-SINAP-100 with a Vario EL Cube elemental analyser. The weight contents of N, C, and H are 9.04%, 39.77%, and 3.775%, respectively, suggesting the presence of DMF and H₂O as solvent species in Th-SINAP-100. The number of DMF molecules in the void was calculated to be four per molecular formula. Thermogravimetric analysis was performed on a NETZSCH STA 449 F3 Jupiter thermal analyzer at a heating rate of 10 °C min⁻¹ under a nitrogen flow, showing an initial solvent loss of 7.24w%, which can be attributed to the departure of four DMF and one H₂O molecules (calcd. 7.16w%) (Supplementary Fig. 11).

The room-temperature values of the absolute oxygen non-stoichiometry (δ) in the La_1.7Ca_0.3Ni_1−yCu_yO_4+δ (y = 0.0–0.4) series were determined from the weight loss detected by the thermogravimetric analysis during the full reduction in a hydrogen-containing atmosphere. This is a traditional method employed for the studies of oxygen non-stoichiometry in oxides with easily reducible transition metal cations (e.g., Refs. [32 (link),36 (link)]). The experiments were performed using a NETZSCH STA 449 F3 Jupiter thermal analyzer (Stuttgart, Germany) on heating in a 50% H₂/50% Ar gas mixture from room temperature to 1000 °C at 10 °C min⁻¹. The procedure resulted in a reduction of the complex oxide to a mixture of metallic nickel and copper co-existing with lanthanum and calcium oxides, as confirmed by the XRD analysis: $${\mathrm{La}}_{1.7}{\mathrm{Ca}}_{0.3}{\mathrm{Ni}}_{1-\mathrm{y}}{\mathrm{Cu}}_{\mathrm{y}}{\mathrm{O}}_{4+\mathsf{\delta }}+\left(1.15+\mathsf{\delta }\right){\mathrm{H}}_2\to 0.85{ \mathrm{La}}_2{\mathrm{O}}_3+0.3 \mathrm{CaO}+\left(1-\mathrm{y}\right) \mathrm{Ni}+\mathrm{y} \mathrm{Cu}+\left(1.15+\mathsf{\delta }\right){ \mathrm{H}}_2\mathrm{O},$$
The value of δ in the initial nickelate was calculated from the change in the weight of the sample as follows: $$\mathsf{\delta }=\left(\frac{{\mathrm{m}}_0}{{\mathrm{m}}_{\mathrm{red}}}{\mathrm{M}}_{\mathrm{red}}-{\mathrm{M}}_{\mathrm{cat}}\right)/{\mathrm{M}}_{\mathrm{O}}-4,$$
where m₀ and m_red are the weight of the initial sample and the reduced sample, respectively, M_red is the molar mass of the reduced sample, M_cat is the molar mass of cations (taking the stoichiometry indexes into account), and M_O is the mass of one mole of oxygen atoms.