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Controlling the morphology of semiconductors at the nanoscale level is the key for efficient photoelectrochemical (PEC) water splitting systems. Herein, we report for the first time the fabrication of porous hematite nanoball array film on conducting FTO via a facile pulse reverse electrodeposition method using cetyltrimethylammonium bromide (CTAB) surfactant and a TiO2 underlayer (UL) on FTO. A prolonged low-temperature-annealing treatment is employed to convert iron into hematite (α-Fe2O3) and to remove the surfactant molecules gradually. Annihilation of surfactant molecules led to the creation of pores during crystallization of hematite nanoballs, thereby providing low-resistant diffusion pathways for the migration and incorporation of cations (Ti4+ from UL and Sn4+ from FTO) in hematite. The hematite photoanode with porous nanoball array exhibited significantly higher PEC performance than the flat hematite due to sixfold enrichment in the donor density, improved charge-transfer properties, and higher light absorption. The enhancement in photocurrent and water oxidation performance of porous hematite photoanode is also feasible when coupled with well-known Co and CoPi catalysts. Thus, our new approach allowed the simple fabrication of hematite films with nanoporous architecture for enabling high photon harvesting and maximized interfacial charge transfer to facilitate water oxidation reaction.

Here, metal oxides/hydroxide (MO = (PdO)n·[Pd(OH)2]m, Co(OH)2, and (PdO)n·[Pd(OH)2]m/CoO, n > m) clusters were successfully co-loaded on the surface of acid-treated molten salt fluxed TiO2 nanorods (ATO-NRs) via conventional wet impregnation. The synergistic effect of palladium oxide/palladium hydroxide and cobalt oxide [((PdO)n·[Pd(OH)2]m/CoO)] co-loading on ATO-NR demonstrated by the photocatalytic degradation of Orange II dye, bisphenol A and S. typhimurium inactivation under mimicked and unfiltered solar light (Xe arc lamp) radiation. Optimum [((PdO)n·[Pd(OH)2]m/CoO)] co-loaded ATO-NRs exhibited significantly higher degradation efficiency (Orange II (91%) and BPA (97%) within 30 min of treatment) over (PdO)n·[Pd(OH)2]m (n > m) and CoO/ATO-NRs under Xe arc lamp light radiation. Also, optimal sample showed higher inactivation efficiency for S. typhimurium than (PdO)n·[Pd(OH)2]m (n > m)/ATO and CoO/ATO-NRs under UVA light radiation, however, the photocatalytic mechanisms for S. typhimurium inactivation was different than the BPA. Photoelectrochemical analyses demonstrated that the significantly accelerated charge-transfer process in metal oxides/hydroxide cluster [(PdO)n·[Pd(OH)2]m/CoO] co-loaded ATO-NRs leading to higher degradation efficiency than other studied samples. Radical trapping supports h+ and O2 − as major reactive species, with OH playing a secondary role in Orange II and BPA degradation. Cell membrane interruption by reactive oxygen species (ROS) and reactions of photocatalyst with the –NH and –COOH group of protein and metalloproteins, nucleic acid in bacterial cells could be the main cause in S. typhimurium disinfection. Plausible charge transport pathways were proposed for photocatalytic degradation of organic pollutants and bacterial inactivation over the (PdO)n·[Pd(OH)2]m/CoO/ATO-NR’s.

Herein, we synthesized porous Zn1-xCdxS nanosheets (PNS)/ZnO nanorod (NR) heterojunction photoanode via self-templated conversion using successively hydrothermal and Cd2+ ion exchange methods. Moreover, after conversion of ZnO to inorganic–organic hybrid ZnS-1,6-hexanediamine (HDA)0.5nanosheets/ZnO NR material, Cd2+ ion exchange was conducted. It was confirmed from X-ray photoelectron spectroscopy (XPS) and Transmission electron microscopy (TEM) analyses that the inorganic–organic hybrid ZnS(HDA)0.5 NS was transformed into Zn1-xCdxS PNS/ZnO NR heterojunction photoanode via the replacement of Zn2+ by Cd2+ ion. Zn1-xCdxS PNS/ZnO NR-160C3H heterojunction photoanode synthesized at 160 °C for 3 h showed the highest photocurrent density of 4.10 mA cm−2 (vs. RHE) under 1.5 G illumination, which was 7.9 times higher than that of bare ZnO NR photoanode. The porous nanostructured morphology and larger surface area of Zn1-xCdxS PNS/ZnO NR heterojunction photoanode fabricated by Cd2+ ion exchange result in efficient light absorption and effective charge transfer pathway. The photoluminescence (PL) and time-resolved photoluminescence (TRPL) results show the shorter lifetime (37 ns) and reduced recombination in Zn1-xCdxS PNS/ZnO NR-160C3H heterojunction photoanode. During PEC analysis, the possible charge transfer mechanism in Zn1-xCdxS PNS/ZnO NR heterojunction photoanode was proposed. Surface passivated Zn1-xCdxS PNS/ZnO NR-160C3H photoanode shows improved photostability and exhibited 3.8 times higher H2 evolution (161 μmol) than the Zn1-xCdxS PNS/ZnO NR-160C3H (42 μmol) photoelectrode at 0.9 V vs. RHE.

To tackle the problem of bulk recombination and to solve the holes diffusion issue in hematite, the shape-guiding and in situ doping is an effective strategy. Herein, we developed a novel strategy for designing and fabricating zirconium-doped transparent hematite (Zr-Fe2O3(I)) photoanode through an in situ hydrothermal method and stoichiometric iron and zirconium dilution. The concentration of ZrO(NO3)2 and FeCl3·6H2O in the precursor solution effectively influenced the transparency and morphology of zirconium-doped Fe2O3. The XPS and TEM analyses confirms the co-existence of Zr doping and surface modification of Fe2O3 nanocoral diffused ZrO2 after high temperature quenching. Synergism between the Zr doping and ZrO2 layer facilizes the charge transfer in Zr-Fe2O3 nanocoral (NC) photoanodes. Among the photoanodes prepared by variously diluted concentrations of the iron and zirconium precursor, the in situ 1/32 Zr-Fe2O3 nanocoral (NC) photoanode achieved an excellent photocurrent density of 1.55 mA cm2 at 1.23 V vs. RHE, which is about doubles than that of the conventional pristine Fe2O3 (P-Fe2O3) NR. Additionally, as result of in situ Zr doping, favorable nanocoral morphology and ZrO2 surface modification exhibits the decreased changer transfer resistance and increased incident photon to current efficiency (IPCE) of 1/32 Zr-Fe2O3 NC upto 21.9%. This in situ Zr-doping and nanocoral morphology 1/32 Zr-Fe2O3 fulfills the requirements of both high charge separation efficiency and improved water oxidation kinetics. A novel 1/32 Zr-Fe2O3 (I) NC photoanode exhibits O2 and H2 evolution up to 69 and 138 μmol during 5 h of overall pure water splitting. This novel in situ hydrothermal dilution approach is feasible for fabricating a transparent hematite photoanode with NC morphology for practical PEC water splitting.

An inorganic–organic CdSe(en)0.5/CdIn2S4/TiO2 complex heterostructure was successfully synthesized using a facile solvothermal method. The morphology of a CdSe(en)0.5/CdIn2S4/TiO2 heterostructure was controlled by varying the concentrations of cadmium nitrate and selenium precursors in ethylenediamine. Intentionally controlling the morphology enhances the absorption within the visible region compared to a ZnIn2S4/TiO2 photoanode. The photoelectrochemical (PEC) study shows that the CdSe(en)0.5/CdIn2S4/TiO2 photoanode complex heterostructure exhibits a photocurrent density of 2.43 mA cm−2 at 0 V versus Ag/AgCl, which is 180% higher than that of a ZnIn2S4/TiO2 photoanode. The extra-delayed lifetime and photostability of CdSe(en)0.5/CdIn2S4/TiO2 complex heterojunction is cause of efficient hole scavenging. During the PEC measurement, the Se and ethylenediamine leaches out into the electrolyte while S2− from the Na2S + Na2SO3 electrolyte reacts with surface of the CdSe(en)0.5/CdIn2S4/TiO2 complex heterojunction. Such structure can effectively separate the charge carrier and yields 100 µmol of hydrogen within 3 h. The possible charge transfer mechanism during solar hydrogen generation in an inorganic–organic CdSe(en)0.5/CdIn2S4/TiO2 complex heterojunction structure has also been proposed.