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6 protocols using titaniumfoil

1

Fabrication of Silver Cubic Nanoparticles and SERS Substrates

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The following chemical
reagents were used to prepare the silver cubic nanoparticles and SERS
substrates: trisodium citrate dihydrate, silver nitrate, potassium
chloride, ethylene glycol, ethanol, acetone (all of the above reagents
were from POCH S.A.), sodium sulfide (Sigma-Aldrich), polyvinylpyrrolidone
(PVP) with an average molar mass of ca. 4 × 104 g/mol
(Fluka), glycerin (Chempur), ammonium fluoride (Chempur), and pyridine
(UniChem). All of the chemicals were used without further purification
or treatment. The water was purified by a Millipore Milli-Q system
and had a resistivity of ca. 18 MΩ/cm11. A titanium
foil (0.25 mm-thick and 99.5% purity) from Alfa Aesar was used to
form the ATO (anodic titanium oxide) layer, and the reference was
a flat SERS substrate cut into 1 cm2 round plates. Before
anodization, all the plates were cleaned ultrasonically with acetone
and ethanol, rinsed with water, and dried in air.
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2

Synthesis and Characterization of Silver Nanoparticles

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Trisodium citrate dihydrate, silver nitrate, potassium chloride, ethylene glycol and acetone were purchased from POCH S.A. (Gliwice, Poland). Sodium sulphide was acquired from Sigma-Aldrich (St. Louis, MO, USA). Polyvinylpyrrolidone (PVP) with an average molar mass of ca. 4 × 104 g mol−1 was purchased from Fluka (Seelze, Germany). Glycerin and ammonium fluoride were purchased from Chempur (Piekary Slaskie, Poland). Pyridine was purchased from Ubichem (Eastleigh, UK). All of the chemicals were used without further purification or treatment. The water was purified by a Millipore Milli-Q system and had a resistivity of ca. 18 MΩ cm−1. The silver used as a material for electrodes was purchased from the Polish Mint (Warsaw, Poland). Titanium foil of 0.25 mm thick and 99, 5% purity was purchased from Alfa Aesar (Kandel, Germany). It was cut into 1 cm2 round plates. The plates were cleaned ultrasonically with acetone and ethanol, rinsed with deionized (DI) water, and dried in air.
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3

Fabrication of TiO2 Nanotube Arrays for TENG

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TiO2 nanotube arrays have been fabricated by anodization of (10 cm × 10 cm), 250 µm Titanium foil (purity 99.5%; Alfa Aesar) in ethylene glycol containing 0.2 vol% H2O and 0.3 M NH4F at 60 V bias voltage in two-electrode electrochemical setup for 100 min at room temperature to get nanotubes with the length of 20 µm. Nanotubes were annealed at 450 °C for 6 h in pure oxygen with heating and cooling rates of 1 °C min−1 to get pure anatase phase. The precise method for fabrication and characterization of self-organized TiO2 nanotubes can be found in our previous publications32 (link),33 (link). The Wettability has been investigated utilizing Dataphysics-OCA setup by recording the contact angle of 2 µL drop on nanotube surface. TENG were fabricated from two layers and operated in vertical contact-separation mode. The static part was fabricated by attaching 2 Mil Kapton@Tape on the Aluminium tape, the contact provided directly through Aluminium tape. The moving parts are is Titanium nanotube array electrode. Electrodes had rectangular shape with the size of 3 cm × 3 cm. The current characterizations were performed using autolab potentiostat (Metrohm Autolab PGSTAT 302N) and the acquired voltages were recorded using 2 GHz Agilent digital oscilloscope. All experiments has been done by home-made atuomatic tapping instrument with the control of force and frequency of tapping.
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4

Conversion of PbO2 to PbI2 Protocol

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Conversion
of the as-deposited PbO2 to PbI2 was carried
out in a 100 mL Erlenmeyer flask with a ground-glass joint (VWR, 29/32).
Hydroiodic acid (20–300 μL, 55%, no stabilizer; Sigma-Aldrich)
was pipetted into a glass boat (l = 5 cm, w = 1 cm), and the boat was transferred into the flask.
A total of 250 mg of silica gel granules (2–6 mm; VWR Chemicals)
was spread around the boat inside the flask to absorb excess water
from the Hydroiodic acid. A substrate holder was bent from a titanium
foil (Alfa Aesar, 0.25 mm, 99.5%) and placed over the boat. The PbO2 films were placed onto the holder facing upward. The flask
was then flushed with nitrogen (99.999%) for 2 min and sealed with
a glass stopper. A pinch clamp and high-vacuum silicone grease were
used to ensure hermetic seal. The assembly was heated in either a
stirred oil bath or an air oven and kept at 90 °C for 90 min
unless otherwise specified. After conversion, the PbI2 films
were removed from the still hot flask.
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5

Fabrication of Titanium Nitride Thin Films

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TiNT was fabricated
on the surface
of titanium foil (0.25 mm thick, 99.5% purity; Alfa Aesar, Tianjin,
China) by anodization.11 (link) The brief process
is as follows: the foil was placed in distilled water, followed by
ultrasonic cleaning in anhydrous ethanol and distilled water for 5
min to remove any contamination. Then, samples were put in mixed acid
[a solution containing 3% (v/v) 70% HNO3 and 2% (v/v) 48%
HF] for another 5 min to remove the oxidation layer on the titanium
surface. The pretreated foil was linked to the anode of the potentiostat,
the counter electrode was made using platinum, and the electrolyte
was created using 1 M H3PO4 with 0.5 wt % HF
at a voltage of 20 V and room temperature (between 15 and 25 °C)
for 3 h. Eventually, after calcination at 450 °C for 3 h, samples
were cut into 1 × 1 cm2 pieces.
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6

Anodization and Characterization of Antimony Tin Oxide (ATO) Nanostructures

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Prior to anodization, a titanium foil (99.5% in purity, 0.25 mm thick, Alfa Aesar) was polished electrochemically, and then chemically [32 (link),34 (link),35 (link)]. Nanostructured ATO layers were synthesized in an ethylene glycol-based solution containing NH4F (0.38 wt.%) and H2O (1.79 wt.%) in a three-step procedure carried out at a constant voltage of 40 V at 20 °C. The first and second anodizing steps lasted for 3 h. After each step, an adhesive tape was used to mechanically remove the obtained oxide layers. The third anodizing step was carried out for 10 min in a freshly prepared electrolyte. During each step, a constant stirring rate of 200 rpm was provided [36 (link)]. As-received amorphous materials were subjected to annealing in air at 400 °C for 2 h with a heating rate of 2 °C min−1 using a muffle furnace (FCF 5SHM Z, Czylok, Poland) [35 (link)]. The morphology of ATO layers was characterized using a field emission scanning electron microscope (SEM, Hitachi S-4700, Japan). The diffraction patterns of ATO were registered using X-ray diffractometer Rigaku Mini Flex II with a Cu Kα radiation (1.54060 Å) at the 2θ range of 20–60°. For the analysis of diffraction patterns, the International Centre for Diffraction Data (ICDD) database was used.
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