Jem 2800

The thin specimens of the CsMPs were observed using a TEM (JEM-2010, JEOL) operated at 200 kV to characterise the inner structures of the CsMPs. EDS analysis was conducted using a STEM (JEM-2800, JEOL) operated at 200 kV equipped with a silicon drift detector (X-Max^N 100 TLE, Oxford Instruments). The probe size and current were ~1 nm and ~1 nA, respectively, and the collection angle (2θ) of the annular dark-field (ADF) detector was 46–208 mrad. Sample thickness measurement using EELS was also conducted using a spectrometer (Enfina, Gatan) attached to the STEM. The collection semi-angle was ca. 27 mrad and the full-width at half-maximum of the zero-loss peak was ca. 1.2 eV.

Morphologies of samples were characterized by scanning electron microscope (SEM, SU3500, HITACHI and MERLIN Compact, ZEISS) and transmission electron microscopy (TEM, JEM‐2800, JEOL and FEI Talos F200X G2, FEI). The crystallographic information was analyzed by X‐ray diffraction (XRD, Ultima IV, Rigaku) equipped with a Cu Kα radiation source. Specific surface areas, pore volume, and pore size of samples were determined using N₂ physisorption isotherms at 77 K (ASAP 2020 PLUS Analyzer, Micromeritic). CO₂ uptake amount were determined at 298 K (ASAP 2020 V4.03, Micromeritic). Metal loadings in the catalysts were determined by inductively coupled plasma optical emission spectrometry (ICP‐OES, SpectroBlue, Spectro). X‐ray photoelectron spectroscopy (XPS, Thermo ESCALAB 250XI, ThermoFisher), The charging effect was corrected using the C1s level (284.8 eV) as the reference. XAFS spectra at the copper K edge and were collected at Australian Synchrotron, ANSTO. Synchrotron powder X‐ray diffraction (Synchrotron PXRD) measurements were measured at PD beamline, Australian Synchrotron, ANSTO with a wavelength of λ = 0.77471 Å. UV–vis absorption diffuse reflectance spectra (UV–vis DRS) were recorded on a Cary 100 UV–vis spectrophotometer using an integrating sphere accessory.

Cells sheets or tissues were fixed overnight at 4 °C in a solution containing 2.5% glutaraldehyde, 1% paraformaldehyde, 100 mM cacodylate buffer at pH 7.4, 6 mM CaCl₂, and 4.8% sucrose. The next day, cells were washed three times for 5 min each with cacodylate buffer, post-fixed with 2% osmium tetroxide at room temperature for 45 min, washed twice for 5 min with cacodylate buffer, then washed once with distilled water for 5 min. Specimens were then stained with saturated uranyl acetate for 45 min at room temperature, washed three times for 5 min each with distilled water, then dehydrated with consecutive ethanol washes (30%, 50%, 70%, twice at 95%, and three times with 100%) for 15 min each. This was followed by dehydration with absolute acetone three times for 10 min each. Specimens were infiltrated with consecutive EPON epoxy resin incubations (30% for 5 h, 70% overnight, three times with 100% for 8 h). 70 nm thick sections were made using a Leica Ultra Cut 6 ultratome, and imaged using a JEOL JEM-2800 operated at an accelerating voltage of 200 kV.

Morphology of amorphous and annealed NTs was observed using a field emission scanning electron microscope (FE-SEM, Hitachi, S-4800). The dimensions (Length, wall thickness, diameter) and uniformity of NTs were analysed using ImageJ software. A total of 10 nanotube dimensions for each sample was measured and the standard deviation for each dimension was also calculated. The crystal phases present within the NTs after annealing were observed using x-ray diffractometer (Rigaku MiniFlex 600) with CuKα radiation (λ = 1.54 A) between 2θ = 20°–80° at a rate of 0.025°/s. The XRD pattern were analysed using PDXL software. The Fast Fourier Transform (FFT) and Selected Area electron Diffraction (SAED) patterns were generated using high resolution transmission electron microscope (S/TEM, JEOL JEM-2800), and were analysed using Gatan, and ImageJ. Raman spectra were produced using micro-Raman spectroscopy (WiTec AlphaSNOM).

All samples were ground in an agate mortar containing a few drops of EtOH. The resulting samples were diluted with EtOH and drop-cast onto 200-mesh copper grids, coated with a carbon film (Rigorous). Subsequently, the samples were dried in an oven at 70 °C. The HR-TEM and ED measurements were carried out at the Electron Microscopy Facility at IST Austria using the S/TEM JEOL JEM2800 instrument with an accelerating voltage of 200 kV equipped with a complementary metal–oxide–semiconductor transmission electron microscopy (TEM) camera (TemCam-XF416) for the HR-TEM images and a 1,024 × 1,024 pixel charge-coupled device camera (Hamamatsu ORCA R2) for the ED images. Although amorphous a_gZIF-62_nP and a_gZIF-62_P display a relatively robust beam tolerance, the crystalline ZIF-62 samples are very beam sensitive. To mitigate the effects of beam damage on ZIF-62, the electron beam was deliberately blocked on identifying the target crystals until the optimal magnification and focus distance were set. Subsequently, snapshots were taken to minimize any potential beam-induced alterations in the samples. The reported interatomic distance distributions were measured using the EM Measure Beta 0.85 software package. Reported values are averaged over a total of 200 counts, consisting of two independent counts of 100 counts per sample.

The crystal structure, morphology and microstructure of the samples were characterized by X–ray diffraction (XRD, D8 Advance, Bruker, Germany), Raman spectroscopy (Raman, LabRAM HR Evolution, Horiba, Japan), scanning electron microscopy (SEM, JSM-7001F, JEOL, Japan), an energy–dispersive X–ray spectrometer (EDX), a transmission electron microscope (TEM, JEM-2800, JEOL, Japan), and X–ray photoelectron spectroscopy (XPS, Scientific K–Alpha, Thermo, Waltham, MA, USA). The Si–NSs content of the samples was measured by thermogravimetric analysis (TGA, 7300, Hitachi, Japan) in the air atmosphere and inductively coupled plasma spectrometer (ICP, 5110, Agilent, Santa Clara, CA, USA). The specific surface area and pore size distribution of the samples were tested by a specific surface area analyzer (BET, ASAP2460, Micromeritics, Norcross, GA, USA).