The Effect of Adding Aluminium on the Performance of ZnO NRs/PANi in Their Application as Photoelectrochemical Water Splitting

Photoelectrochemical (PEC) is a new renewable energy technology that converts H 2 O into hydrogen and oxygen gas with the help of sunlight. A photoelectrochemical cell device consists of three main components, one of which is the photoanode. One of the materials that can be used as a photoanode is ZnO which has good electrical properties and is non-toxic. Nanorods-structured ZnO has the advantage of being able to increase light absorption due to its high surface area. However, the resulting performance is still quite low. So it is necessary to make modifications to the photoanode, one of which is by adding aluminium material to ZnO NRs, which has the potential to increase the conductivity of PEC in the production of H 2 and O 2 in H 2 O. To overcome the loss of samples during testing, the thin film will be coated with conductive polymers such as polyaniline (PANi), which has high conductivity, can increase photoactive ability, and has good corrosion resistance. In this study, the performance of ZnO NRs/PANi against AZO NRs/PANi will be studied by adding aluminium. The ZnO nanorods were synthesized by Hydrothermal method, Aluminium was deposited on ZnO NRs by DC Magnetron Sputtering method, and PANi was synthesized by polymerization method. From the XRD characterization results, it can be concluded that the addition of aluminium to ZnO NRs/PANi causes an increase in crystallinity and peak shift. SEM characterization shows that the addition of Al to ZnO NRs/PANi causes the porosity value to increase. In addition, UV-Vis characterization showed that the addition of Al material to the ZnO NRs/PANi thin film resulted in a wider range of absorbance of the light spectrum. Then, Cyclic Voltammetry test shows that the addition of aluminium increases the efficiency of the photoelectrochemical.


I. Introduction
Photoelectrochemical (PEC) is a technology that converts light energy into electrical energy through electrolysis [1]- [3].Photoelectrochemical technology has a significant impact because utilizing this technology can produce clean and sustainable electrical energy [4].So that development of photoelectrochemical technology can also reduce the cost of energy production to be more affordable [5].One of the most important constituent components that plays a role in converting photons into electron-hole pairs, namely the photoanode [6].Semiconductor materials commonly used as photoanode constituents include TiO2, ZnO, WO3, and CuO [7].Among these materials, ZnO has the potential as an anode constituent material because of its advantages of having good electrical properties, non-toxicity, easy fabrication, and large binding energy of 60 meV [8]- [10].ZnO nanostructures such as ZnO nanorods were chosen because they have high electron mobility [11], an energy band gap of ~3.37 eV [8], good photocatalyst activity, and structural stability [12].ZnO nanorods-based PEC research conducted by Tan et al., produced a current density of up to 0.483 mA/cm 2 [13].
Research on ZnO NRs/Au-based PEC technology produced a current density of 30 µA/cm 2 [14].Other research on ZnO/Fe3O4 still produces a fairly low current density of 70 µA/cm 2 [15].However, the resulting performance is still quite low.Therefore, to obtain high performance and highly to splitting of H2O into H2 and O2, the addition of metal materials with elements such as Al, N, Mg, and Cd [16].So in this study, modifications were made to the photoanode by adding aluminium material to ZnO NRs which has the potential to increase the conductivity of PEC in the production of H2 and O2 in H2O.Among other metal materials, Aluminium (Al) has a very high potential to be developed because of its high stability and is able to reduce the resistivity of ZnO [17].Research by Shet et al. on Photoelectrochemical based ZnO NRs/Al (AZO NRs) with RF Magnetron Sputtering method at 300 W power variation produces the highest current density, namely 0.36 mA/cm 2 [18].Another study by Zong et al. on solar cells based on ZnO NRs/Al, SiO2 with the Co-Sputtering method at a power variation of 25 W obtained the highest current density results of 0.37 mA/cm 2 [19].Recent research conducted by Rabell et al. regarding Photoelectrochemical proved that increasing the addition of Al to ZnO (AZO) made the photocatalytic activity for producing hydrogen gas higher [16].
However, so far during the photoelectrochemical performance testing process, sample loss often occurs.Sample loss during the testing process can affect the stability and lifetime of the photoanode.So, this can be overcome by adding conductive polymers to the ZnO NRs and AZO NRs photoanode.A conductive polymer is a type of polymer that has electronic and optical properties like metals and mechanical properties like polymers.One of the reasons for using conductive polymers in PEC cells is that they can increase the photoactive ability, efficiency, and corrosion resistance of the sample [20], [21].PANi is a polymer with high conductivity [22] and has good environmental stability [23].Research related to conductive polymers in PEC cells has been carried out.It was reported that ZnO/PANi increased the breakdown of H2O into H2 and O2 in wastewater [24].Polyaniline was reported to increase the photosensitivity of PEC to visible light [23].Therefore, a study will be carried out on the addition of aluminium to ZnO NRs/PANi as a fuel cell photoanode which is expected to produce high performance.

Synthesis of Photoanode
In this research, there are several steps involved.The ZnO nanorods were synthesized in two steps by coating ZnO seed layer on ITO glass using spin-coating method and growing ZnO nanorods by hydrothermal method.Zinc Acetate Dihydrate powder (0.88 g) was dissolved with 20 mL of ethanol p.a. Stirred for 30 minutes with a solution temperature of 70°C.Then add Monoethanolamine (MEA) 0.24 μL and strirer for 1 hour.Deposition on ITO Glass by Spin coating method, then annealing the film at 400°C for 2 hours.The precursors used to grow ZnO nanorods were synthesized from Zinc Nitrate Tetrahydrate (0.58 g) and HMTA (0.32 g) were dissolved with 50 mL DI water.After that, stir the solution for 45 minutes at room temperature.The ZnO seed layer film was immersed in the precursor solution for 5 hours at 155°C.Then annealing it films for 2 hours at 550°C.Furthermore, additional material aluminium (Al) was coated by DC Magnetron Sputtering method.Aluminium metal material was deposited on ZnO NRs by DC Magnetron Sputtering method.Aluminium sputtering was carried out for 15 minutes with 80 W power.After that, the sample was annealed at 150°C for 30 minutes.In addition, to synthesize PANI it is done by dissolving 1.82 mL Aniline in 0.603 mL of HCl (1 M).At the same time 5.71 grams of Ammonium Peroxidisulfate [(NH)4S2O8] was dissolved in 50 mL of distilled water.Both solutions were allowed to stand for 1 hour.Then the two solutions were mixed and stirred at 600 rpm for 1 hour.Then allowed to stand for 24 hours until a precipitate formed.Then washed until pH 7. Finally dried in oven at 100 ºC for 40 minutes.To coat the PANi polymer, the spin coating method was carried out at a speed of 3000 rpm for 1 minute.Then ZnO NRs/PANi and AZO NRs/PANi film as photoanodes was annealed at 100°C for 1 hour.

Cyclic Voltammetry Testing
The ability of the sample was tested using Cyclic Voltammetry (CV) testing scheme of three electrodes in bright conditions with a power of 100 mW on a sample with an active area of 1 cm 2 .The electrolyte used was 0.1 M Na2SO4.In the test, the sample (ZnO NRs/PANi & AZO NRs/PANi) acts as working electrode, platinum electrode as counter electrode, and Ag/AgCl as reference electrode.CV testing was carried out with scan rates of 50 and 100 mV/s.

Characterization
There were several characterizations performed in this study, including XRD, SEM, and UV-Vis.X-ray Diffraction (XRD) analysis was performed using PanAnalytical Expert Pro with a diffraction angle of 20 − 80°.Then, Scanning Electron Microscope (SEM) analysis was carried out to analyse the morphology of the sample both from its surface structure with a magnification of 50,000 times and from a cross-section with a magnification of 100,000 times.SEM analysis was carried out using FEI type INSPECT-S50.Furthermore, UV-Vis Spectrophotometer analysis was carried out to determine the absorbance and band gap of the material.UV-Vis analysis was carried out at a wavelength of 200-800 nm using Analytic Jena Specord 200 plus.
Figure 2 shows the 2θ positions of the three main peaks of the ZnO NRs/PANi and AZO NRs/PANi film diffraction pattern in the hkl (100), (002), and (101) planes.It is shown in Table 1 that there has been a shift in the positions of the three peaks.This shift is known to occur due to shrinkage of the ZnO nanorods lattice.This is because the Zn 2+ atom which has a radius of 0.74 Å, is replaced by an Al 3+ atom which has a radius of only 0.53Å [25].The morphology of the samples can be identified from the Scanning Electron Microscopy (SEM) characterization results.Figure 3 shows the surface morphology of ZnO nanorods (ZnO NRs) and AZO nanorods (AZO NRs) shown from SEM results with a magnification of 50,000 times.Based on the SEM results as shown in Figure 3 (a), ZnO NRs have a hexagonal wurtzite structure with a fairly even distribution and have a growth direction perpendicular to the ITO substrate surface.This is in accordance with research conducted by Abadi et al [15].The addition of Aluminium material on ZnO NRs results in surface morphology that tends to be rough.The rough surface of AZO NRs is caused by the merging of grain boundaries between ZnO and Al [26].In addition, the SEM characterization results can also be used to determine the porosity value as seen from the surface morphology of the material.Figure 5 is a three-dimensional graph of the porosity distribution of ZnO NRs/PANi and AZO NRs/PANi thin films.
The porosity value is the ratio between the empty volume and the total volume of the entire sample.The higher porosity value indicates that the greater the volume of space not occupied by AZO NRs/PANi [28].Based on the calculation of the porosity value, it is found that the addition of Al material to ZnO NRs/PANi can increase the porosity of the thin film.This is also in accordance with research conducted by Hong et al, where an increase in porosity occurs because aluminium can inhibit the growth of ZnO grains [29].In addition, the high porosity value also indicates that the active surface area produced is larger, so as to improve the performance of the photoanode in photoelectrochemical [30].The results of porosity values are presented in Table 2.
Furthermore, to determine the band gap value of material, the optical band gap calculation is carried out using the Tauc plot method.The following is the Tauc plot equation (1) [33]: The value of α is the absorption coefficient of the material, h is the Planck constant, v is the frequency of the incident photon, while A is the energy constant, and Eg is the band gap energy value.The results of the band gap energy calculation of the film base materials, ZnO NRs and PANi, are shown in Figures 7(a) and 7(b).In addition, the calculation of the band gap energy value is also carried out to determine the difference when ZnO NRs/PANi is added with Aluminium.From the Tauc Plot fitting results, it can be seen that the addition of Al material to ZnO NRs/PANi results in an increase in band gap energy [33].Furthermore, the fitting results of ZnO NRs/PANi and AZO NRs/PANi thin films are shown in Figures 7(c   Based on the results of the data analysis presented in Table 3, it shows that the absorbance value of light is inversely proportional to the band gap energy value obtained.The AZO NRs/PANi thin film experiences a blue shift in its band gap when compared to ZnO NRs/PANi [34].In general, the band gap in semiconductors is affected by the Burstein-Moss effect, compressive strain, and Urbach tail shift [35], [36].The increase in the band gap of ZnO NRs when added with aluminium (Al) is due to the reduction in pressure [37].This band gap increase is also influenced by the Burstein-Moss effect where aluminium shifts the Fermi level to the conduction band [38].
Based on the CV test results, a graph between current density and bias voltage was obtained, as shown in Figure 8. From Figure 8, it is known that the addition of Al material to ZnO NRs results in a higher current density.It is also proportional to the efficiency or performance of the photoelectrochemical cell.In the three-electrode testing scheme, the efficiency value can be calculated using Equation (2) [39]: Where, (Vapp) is the efficiency calculated when using the bias voltage.I(Vapp) is the current produced.∆ adalah Gibbs free energy based on the breakdown of water molecules is 1.23 V. V is the max voltage applied,  is the Faraday efficiency which is 100%.P is the beam power used per unit area and A is the active area of the sample [39].The photoelectrochemical water splitting performance results obtained are higher than the PEC research conducted by Abadi et al. with ZnO NRs/Au/PANi photoanodes which produced a current density of 10.6 μA/cm 2 with a performance of 0.16% [40].This research has also been proven by Rabell et al.where the addition of aluminium to ZnO as a photoelectrochemical is able to increase the breakdown of H2O into H2 and O2 higher [16].So it can be concluded that the addition of aluminium to ZnO is considered capable of improving the performance of photoelectrochemical cells, as evidenced by the increase in the efficiency value of the photoelectrochemical cell.In addition, the addition of PANi conductive polymer is also able to increase the current density value and prevent loss during the testing process so that it has good stability and lifetime.

IV. Conclusions
The addition of aluminium to ZnO NRs/PANi causes an increase in crystallinity and a peak shift.The results from SEM also show that the addition of Al to ZnO NRs/PANi causes the thickness of the thin film to increase and increases the porosity value.Apart from that, the UV-Vis characterization shows that the absorbance decreases, but the addition of Al material to the ZnO NRs/PANi thin film results in a wider range of absorption (absorbance) of the light spectrum.This result shows that the sample is only able to absorb UV light.For the ZnO NRs/PANi band gap, when aluminium is added, it increases.This increase in band gap energy may be attributed to the Burstein-Moss effect where Aluminium shifts theFermi level to the conduction band.Then, from Cyclic Voltammetry results obtained, it shows that the addition of aluminium material to the ZnO NRs/PANi thin film can produce a photoelectrochemical cell photoanode with better performance for application as a fuel cell in PEC Water Splitting technology.

Table 1 .
Diffraction angle shift of the first three peaks of thin film

Table 3 .
Absorbance value and band gap energy of ZnO NRs/PANi & AZO NRs/PANi Thin Films

Table 4 .
Current density and efficiency performance of CV test results