Supporting Information for

Humidity Sensing and LED assisted photocatalytic performance of Ag-incorporated

ZnFe2O4 Nanoparticle embedded on the surface of reduced graphene oxide nanosheets
Moksodur Rahman, Md. Lutfor Rahman*, Bristy Biswas, Md. Farid Ahmed, Md. Aftab Ali
Shaikh, Shirin Akter Jahan, Nahid Sharmin
Institute of Glass and Ceramic Research and Testing (IGCRT), Bangladesh Council of Scientific
and Industrial Research (BCSIR), Dhanmondi, Dhaka-1205, Bangladesh.
*Corresponding Author: [email protected]; [email protected];
[email protected]

1. Synthesis of GO. In conventional procedure, Graphite (3.5 g) and sodium nitrate (1.75 g) were
dispersed in concentrated (98%) sulphuric acid (100 mL). The dispersion was cooled to about ~5
°C using ice bath and stirred for 2.5 hours. After that, over a period of 2.5 hours, potassium
permanganate (12 g) was added and continuously stirred for another 2 h. The cooling bath was
then removed and the mixture was kept to room temperature.

After that, ~120 mL of distilled water was added (gas evolved) over a period of an hours and the
temperature was increased to ~90°C in water bath. After reaching ~90 °C, 320 mL of water was
added again and continuously stirred for 1.5 hour to obtained mud brown suspension. Then above
mixture was treated with 30% H2O2 and ~4 liters of warm distilled water were added to diluted
the mixture. This precipitate was allowed to settle down under the action of gravity. After 24 h the
resultant clear solution at the top was decanted slowly. To eliminate the excess manganese and
sulfate ions from the product, 2M HCl was then added to the mixture. The obtained suspension
was repeatedly cleaned using high-speed centrifugation and distilled water until pH ~7 was
attained. Finally, GO was obtained after the filtration and the product was stored for a several days
in a vacuum desiccator over silica-gel before characterization and used in composite.
Figure S1. Preparation step of Graphene Oxide by modified Hummer method.

Figure S2. Preparation step of Ag@ZnFe2O4/rGO by Hydrothermal method

Figure S3. Fabrication of Lab made (a) Closed humidity measurement chamber, and (b)
Photocatalytic Chamber.

2. Characterization. The powder X-ray diffraction (PXRD) analysis was performed on a Rigaku
(SmartLab SE) diffractometer using high-intensity Cu Kα radiation (λ = 1.5406 Å) in the range of
5−70 ° (2θ) to investigate the crystallinity and crystallographic phases of the obtained products.
The Peak profile analysis procedure and equation

From PXRD data, the peak profile analysis carried out by following parameters:

The average crystallite sizes were measured using following classical Scherrer (DC-S) method [1]:

DC−S = 0.9λ/(βhkl ∙ cosθ) (1)

Where, λ equal to X-ray wavelength, βhkl is the full width at half maximum (FWHM) intensity of
the respective miller indices and 𝜃 equivalents to Bragg angle.

Munshi-Scherrer equation also obtained by rearranging Eq. (1) and taking logarithm on both sides
as follows [2]:

lnβhkl = ln (0.9λ⁄𝐷 ) + ln(1⁄cosθ) (2)

𝑀−𝑆

DM−S = 0.9λ/eintercept (3)

With the help of Eq. (2) and (3) crystallite size was calculated using intercept, which obtained by
linear plot of ln(1/cosθ) along X-axis and lnβ along Y-axis.
 Figure S4. Munshi-Scherrer plots of (a) ZnFe2O4, (b) ZnFe2O4/rGO, (c) Ag@ZnFe2O4/rGO.

The average crystallite size also estimated using Williamson-Hall (W-H) model [2].

Βhkl ∙ cosθ = 0.9λ/DW−H + 4ε ∙ sinθ (4)

The intercept of the fitted line will be obtained by linear plot of βcosθ along Y-axis and 4sinθ

along X-axis. Crystallite size estimated from intercept using Eq. (5) as follows:

DW−H = 0.9λ/intercept (5)

 Figure S5. Williamson-Hall plots of (e) ZnFe2O4, (f) ZnFe2O4/rGO, (g) Ag@ZnFe2O4/rGO.

The Size-Strain Plot (SSP) model also used to evaluate the crystallite size by following

Equations (6-7) [3].

2
(Dhkl βhkl cosθ)2 = kλ⁄D (d2hkl βhkl cosθ) + (ε⁄2) (6)

DSSP = 0.9λ/Slope (7)

The slope of the fitted line will be obtained by plot of (dβcosθ)2 with respect to (d2βcosθ), which

gives the crystallite size .

 Figure S6. Size-Strain plots of (a) ZnFe2O4, (b) ZnFe2O4/rGO, (c) Ag@ZnFe2O4/rGO.

Halder-Wagner model is another technique which gives crystallite size precisely by given Eq.

(8)[4]:

2
βhkl⁄ kλ βhkl⁄ 2
( tanθ = ( ⁄DH−W ) (
) tanθ cosθ) + 16ε (8)

A linear fit graph is made by plotting of (βhkl/tanθ)2 versus (βhkl/tanθ cosθ) and obtained slope

gives Halder-Wagner crystallite size.

 Figure S7. Halder-Wagner plots of (e) ZnFe2O4, (f) ZnFe2O4/rGO, (g) Ag@ZnFe2O4/rGO.

Lattice constant ‘a’ was calculated using Eq. (9)

𝑎 = 𝑑ℎ𝑘𝑙 √ℎ2 + 𝑘 2 + 𝑙 2 (9)

Surface area and lattice strain (Ɛ) of the prepared sample was estimated using the following Eq.
10-11 [5].

𝑆 = 6/𝐷𝐶−𝑆 ∙ ϱx (10)
 𝜀 = 𝛽ℎ𝑘𝑙 /𝑡𝑎𝑛𝜃 (11)

The x-ray density (ϱx) was calculated from the values of the lattice parameter using the following
relation [5]:

ϱx = 8M⁄Na3 (12)

where 8 signifies the number of molecules in a unit cell of spinel ferrites lattice. M, N and a is
molecular weight, Avogadro’s number, and the lattice parameter, respectively.

The Bulk density (ϱb) were calculated from the values of pellets parameter by using the following
equation [6]:

𝜚𝑏 = 𝑚/𝜋𝑟 2 𝑡 (13)

Where, m, r, and t is the weight, radius, and thickness of pellets respectively.

The percentage porosity (P) of the samples was determined using the formula:

bulk density
P = 1−( ⁄x − ray density) (14)

By using PXRD data various tetrahedral (A-sites) and octahedral (B-sites) parameter such as ionic
radii (IrA, IrB), bond length (BLA–O, BLB–O), and hoping length (HLA, HLB) also calculated using
Eq. (15-16), (17-18), and (19-20), respectively [7–9].

𝐼rA = (u − 1⁄4)a√3 − r(O2− ) (15)

𝐼rB = (5⁄8 − u)a − r(O2− ) (16)

Bond length, BLA−O = (u − 1⁄4)a√3 (17)

Bond length, 𝐵𝐿𝐵−𝑂 = (5⁄8 − u)a (18)

𝐻LA = a√3/4 (19)

𝐻LB = a√2/4 (20)

where a denotes the lattice constant, r(O2−) signifies the radius of the oxygen ion (0.135 nm), and
u is the oxygen ion parameter (0.375) for an ideal spinel ferrite.
The surface morphology of the products was observed by Transmission electron microscopy
(TEM) ( JEM-2100 plus, Jeol, Japan) observation and elemental analysis were investigated by
energy-dispersive spectroscopy, which was carried out with a - microscope operated at an
accelerating voltage of 15 kV. Particle size distribution was estimated by dynamic light scattering
method using Zetasizer (SZ-100, HORIBA Scientific Ltd, Japan) and Laser diffraction method
using Malvern particle size analyzer (Mastersizer 3000, UK). Prior to analysis samples were
dispersed in deionized water and ultrasonicated for 15 min. The magnetic properties of the
obtained samples were analyzed at room temperature (RT) using vibrating Sample Magnetometer
(VSM-8600, lakeshore, USA) at a highest applied field of 15 kOe. Diffuse reflectance
spectroscopy (DRS) was performed at room temperature with a Perkin-Elmer (model: Lamda
1050+) spectrophotometer in the 280–780nm range. Reflectance (𝑅∞ ) was converted to
absorbance (F(R)) by the Kubelka–Munk equation: F(R) = (1 − 𝑅∞ )2 /2𝑅∞ . Values of Eg are
obtained by extrapolating the linear part of the [FR(hϑ)]n Vs. hϑ plot to the photon energy axis.
The dielectric and electrical properties of the obtained materials were investigated by impedance
analyzer (65120B, Wayne Kerr Electronics, UK) in the frequency range from 100 Hz to 20 MHz
at RT using dielectric measurement fixture. The powder was homogenized by mortar-pestle and
the powder was pelletized at 13 mm diameter by a press machine using 5 KN pressure.
Figure S8. EDS spectrum of (a) ZnFe2O4, (b) ZnFe2O4/rGO, (c) Ag@ZnFe2O4/rGO.
Figure S9. Particle size distribution measured by (a) DLS, and (b) LD

Figure S10. Room temperature magnetization curves of ZnFe2O4, ZnFe2O4/rGO and Ag

@ZnFe2O4 /rGO nanocomposite
Figure S11. Frequency dependent real part of dielectric constant (ε′) fitted with the modified
Debye model taking the spreading factor (α).

Figure S12. Long-term stability of the sensor at (a) 33% RH and (b) 98% RH
Figure S13. (a-b) Degradation performance of Ag@ZnFe2O4/rGO against RhB, and (c-d)
Degradation of MB by trapping of superoxide radicals, holes, and hydroxide radicals (reactive
species) for Ag@ZnFe2O4/rGO catalyst.
Figure S14. PXRD pattern of retrieved catalyst after sixth-cycle.
Figure S15. FT-IR Spectra of used and fresh Ag@ZnFe2O4/rGO photocatalyst.
Figure S16. FESEM micrograph of used and fresh Ag@ZnFe2O4/rGO photocatalyst.

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