Thin Film Photoanodes Research Articles

Efficient CO2 reduction to C2 products in a Ce-TiO2 photoanode-driven photoelectrocatalysis system using a Bnanometer Cu2O cathode

Excessive emission of CO2 into the atmosphere has caused significant environmental issues. Photoelectrocatalytic (PEC) reduction of CO2 is an effective method that combines the benefits of both photo- and electrocatalysis. This process effectively minimizes CO2 emissions, enhances the efficiency of CO2 reduction, and diminishes energy consumption during the reduction process. In this work, we have successfully developed a photoelectrochemical (PEC) system, integrating a Ce-doped TiO2 film as the photoanode and Cu2O as the dark cathode, in which the 4 % Ce-TiO2 film photoanode demonstrated the best performance. Electrochemical performance data revealed that the Cu2O catalysts, characterized by their octahedral geometry that optimally presents active sites for CO2 reduction, displayed superior activity in converting CO2. Through a straightforward hydrothermal synthesis, we crafted three-dimensional, flower-like TiO2 thin films. The strategic incorporation of cerium into the TiO2 matrix not only enhanced the material's crystallinity but also resulted in a uniform and compact morphology. This modification significantly narrowed the band gap of TiO2, thereby boosting its photocatalytic capabilities. In the system where a 4 % Ce-TiO2 thin film photoanode was used to drive the PEC reduction of CO2, the octahedral Cu2O catalyst demonstrated the highest selectivity for C2 products. This occurred at a reaction voltage of −1.4 V vs. RHE, resulting in a total Faraday efficiency of 67.33 %. Notably, this Faraday efficiency is double the one produced from the electrocatalytic (EC) system. This work demonstrates that the use of a 4 % Ce-TiO2 film as a photoanode is able to solve the photocorrosion problem of the Cu2O catalyst while employing a photovoltaic combination to enhance the selectivity to C2 products.

High transmittance BiVO4 thin-film photoanodes by reactive magnetron sputtering for a photovoltaic-photoelectrocatalysis water splitting system

As the system with the highest solar hydrogen conversion efficiency, the further improvement of photovoltaic-photoelectrocatalysis (PV-PEC) efficiency is dependent on the light transmittance, activity and stability of the photoanode. Here, a highly permeable BiVO4 thin film was fabricated through controlled magnetron sputtering. The thickness of the thin film was merely 345 nm, while its transmittance in the visible light range reached as high as 70%. Moreover, large-scale production of such films could be achieved. By incorporating NiFeOx oxygen extraction cocatalyst, under AM 1.5G illumination, the photocurrent density at 1.23 V on reversible hydrogen electrode (RHE) increased to 4.2 mA cm−2 and the incident photon-current conversion efficiency reached 70%. A PV-PEC system was designed to efficiently harness sunlight by integrating the photoanode with a solar photovoltaic panel. Upon connection with the solar photovoltaic panel (with an efficiency of only 7%), spontaneous water decomposition could be achieved, resulting in a solar-to-hydrogen conversion efficiency (ηSTH) of 4.2% for the series system. This study contributes to the realization of cost-effective and highly efficient PV-PEC hydrogen production.

Laser-Printed Photoanode: Femtosecond Laser-Induced Crystalline Phase Transformation of WO3 Nanorods for Space-Efficient and Flexible Thin-Film Solar Water-Splitting Cells.

Despite its potential for clean hydrogen harvesting, photoelectrochemical (PEC) water-splitting cells face challenges in commercialization, particularly related its harvesting performance and productivity at an industrial scale. Herein, a facile fabrication method of flexible thin-film photoanode for PEC water-splitting to overcome these limitations, based on laser processing technologies, is proposed. Laser-induced graphene, a carbon structure produced through direct laser writing carbonization (DLWC), plays a dual role: a flexible and stable current collector and a substrate for the hydrothermal synthesis of tungsten trioxide (WO3) nanorods (NRs). To facilitate water-splitting, a femtosecond-pulsed laser (fs laser) is focused on the WO3 NRs, converting their crystalline phase from pristine orthorhombic to monoclinic structure without thermal damage. With NiFe layered double hydroxide (LDH) catalyst, the flexible thin-film photoanode exhibits good PEC performance (1.46mAcm-2 at 1.23 VRHE) and retains ≈90% of its performance after 3000 bending cycles. With its excellent mechanical properties, the flexible photoanode can be operated in various shapes with different curvatures, enabling space-efficient PEC water-splitting by loading larger photoanode within a given space. This study is expected to contribute to the advancement of large-scale solar water-splitting cells, introducing a new approach to enhance H2/O2 production and expand its application range.

Combined experimental and DFT investigation on photovoltaic performance of low-cost metal-free organic dye-sensitized solar cells

Metal-free organic dyes, viz. eosin yellow (eosin-Y), fluorescein and curcumin were used as sensitizers in zinc oxide (ZnO) nanoparticles thin film photoanode based dye-sensitized solar cell (DSSC) and also investigated by density functional theory (DFT). UV–vis spectrophotometer was employed to determine absorption feature of dyes in solar spectrum, adsorption tendency towards ZnO photoanode surface, molar-extinction coefficient and desorbed dye molecules from the photoanode surface. The photovoltaic performance of metal-free organic DSSCs employing imidazole based liquid electrolyte and platinum counter electrode was evaluated under standard light exposure of 85 mW/cm2. Among the dyes, eosin-Y DSSC delivered overall energy conversion efficiency (η) of 0.95 % with short-circuit photocurrent density (Jsc) of 2.98 mA cm−2, open-circuit photovoltage (Voc) of 0.54 V and fill factor (FF) of 0.50, which was about 20 % and 40 % higher than that of the energy conversion efficiency of DSSCs sensitized with fluorescein and curcumin dyes, respectively. The better photovoltaic performance exhibited by the eosin-Y DSSC is credited to its high molar extinction coefficient, intense light absorption in the solar spectrum and good adsorption on ZnO thin film photoanode surface. The maximum driving force for dye molecules regeneration and electron injection value of eosin-Y dye attached on the surface of ZnO cluster (eosin-Y + ZnO) resulted in higher Voc. The outcomes of this experimental data are in well agreement with DFT results.

Enhanced Photoelectrochemical Performance Using Cobalt-Catalyst-Loaded PVD/RF-Engineered WO3 Photoelectrodes

Critical to boosting photoelectrochemical (PEC) performance is improving visible light absorption, accelerating carrier separation, and reducing electron–hole pair recombination. In this investigation, the PVD/RF method was employed to fabricate WO3 thin films that were subsequently treated using the surface treatment process, and the film surface was modified by introducing varying concentrations of cobalt nanoparticles, a non-noble metal, as an effective Co catalyst. The results show that the impact of loaded cobalt nanoparticles on the film surface can explain the extended absorption spectrum of visible light, efficiently capturing photogenerated electrons. This leads to an increased concentration of charge carriers, promoting a faster rate of carrier separation and enhancing interface charge transfer efficiency. Compared with a pristine WO3 thin film photoanode, the photocurrent of the as-prepared Co/WO3 films shows a higher PEC activity, with more than a one-fold increase in photocurrent density from 1.020 mA/cm2 to 1.485 mA/cm2 under simulated solar radiation. The phase, crystallinity, and surface of the prepared films were analysed using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The PVD/RF method, scanning electron microscopy (FE-SEM), and high-resolution transmission electron microscopy (HR-TEM) were employed to assess the surface morphology of the fabricated film electrode. Optical properties were studied using UV–vis absorbance spectroscopy. Simultaneously, the photoelectrochemical properties of both films were evaluated using linear sweep voltammetry and electrochemical impedance spectroscopy (EIS). These results offer a valuable reference for designing high-performance photoanodes on a large scale for photoelectrochemical (PEC) applications.

Characterization of the electronic structure of sputter-deposited Mo-doped BiVO4 thin-film photoanodes

Molybdenum (Mo) doping is a pivotal strategy to enhance the performance of bismuth vanadate (BiVO4) photoanodes in photoelectrochemical (PEC) devices. This research explores the effects of Mo-doping on BiVO4’s electronic properties, uncovering mechanisms behind improved PEC behavior. Mo-doped BiVO4 was produced via single-target RF sputtering, leading to films with increased photocurrent density. Optimal results were achieved with a 3% atomic ratio of Mo and 15% oxygen partial pressure during deposition. Analysis of the local structure revealed Mo6+ substituting V in the BiVO4 host. Mo doping introduced defect states within the VB, partially occupying the d-band of V4+ and creating additional electron states, causing the fermi level to shift from 1.75 to 2.19 eV from the VB edge. This study underscores the adaptability of Mo-doping in shaping BiVO4’s electronic characteristics, opening new pathways in advanced energy conversion technologies.

SrTiO3 thin film photoanodes fabricated by combinatorial chemical beam vapour deposition: intricate connection between elemental composition and thin films' properties

In this research, we highlight an innovative combinatorial approach to explore the correlation between the elemental composition of SrTiO3 thin films and their photoelectrochemical characteristics for water splitting.

Sn-Doped Hematite Films as Photoanodes for Photoelectrochemical Alcohol Oxidation

Here, the modification of semiconductor thin film hematite photoanode by doping with Sn ions is reported. Undoped and Sn-doped hematite films are fabricated by the electrochemical deposition of FeOOH from aqueous alkaline electrolyte, followed by calcination in air. The photoanodes were tested in photoelectrocatalytic oxidation of water, methanol, ethylene glycol, and glycerol. It is shown that modification by tin dramatically increased the activity of hematite in the photoelectrochemical oxidation of alcohols upon visible light irradiation. The photoelectrocatalytic activity of Sn-modified hematite increased in the sequence of: H2O < MeOH < C2H2(OH)2 < C3H5(OH)3. The quantum yield of photocurrent in the oxidation of alcohols reached 10%. The relatively low photocurrent yield was ascribed to the recombination of photoexcited holes within the hematite layer and on surface states located at the hematite/electrolyte interface. Intensity-modulated photocurrent spectroscopy (IMPS) was used to quantify the recombination losses of holes via surface states. The IMPS results suggested that the hole acceptor in the electrolyte (alcohol) influences photocurrent both by changing the charge transfer rate in the photoelectrooxidation process and by the efficient suppression of the surface recombination of generated holes. Thin-film Sn-modified hematite photoanodes are promising instruments for the photoelectrochemical degradation of organic pollutants.

Ni(II)-doped CuWO4 photoanodes with enhanced photoelectrocatalytic activity

CuWO4 has emerged in the last years as a ternary metal oxide material for photoanodes application in photoelectrochemical cells, thanks to its relatively narrow band gap, high stability and selectivity toward the oxygen evolution reaction, though largely limited by its poor charge separation efficiency. Aiming at overcoming this limitation, we investigate here the effects that Cu(II) ion substitution has on the photoelectrocatalytic (PEC) performance of copper tungstate. Optically transparent CuWO4 thin-film photoanodes, prepared via spin coating and containing different amounts of Ni(II) ions, were fully characterized via UV–Vis spectroscopy, XRD and SEM analyses, and their PEC performance was tested via linear sweep voltammetry, incident photon to current efficiency and internal quantum efficiency analyses. From tests performed in the presence of a hole scavenger-containing electrolyte, the charge injection and separation efficiencies of the electrodes were also calculated. Pure-phase crystalline and/or heterojunction materials were obtained with higher PEC performance compared to pure CuWO4, mainly due to a significantly enhanced charge separation efficiency in the bulk of the material.Graphic abstract

The Photoelectrochemical Response of PbCrO4 Thin Film Fabricated Using Pechini Method: The Effect of Nitrate Decomposition in Precursor Solution

PbCrO4 is one of the metal-oxide semiconductors that can be utilized for photoelectrochemical water oxidation. The Pechini method was employed to fabricate a PbCrO4 thin film photoanode, and the properties of the thin film were found to be dependent on the precursor heating temperature. Precursor heating enhanced the complexation between the metal ion and citric acid and the decomposition of metal nitrate in the Pechini precursor solution, leading to the fine morphology of the film. As the precursor heating temperature increased, the grain size of the film decreased, which lowered the photoresponse for precursor heating temperatures above 80 °C. Meanwhile, at a low precursor heating temperature, the presence of the Urbach tail was confirmed via UV–vis absorption spectroscopy. It can act as a trap, capturing the charge carrier, and leading to the decrease in the photoresponse of the PbCrO4 thin film. Consequently, the photoactivity of the PbCrO4 thin film toward water oxidation was maximized for a precursor heating temperature of 80 °C. However, the performance of the PbCrO4 photoanode degraded during water oxidation, regardless of the precursor heating temperature.

Thin-Film Nanocrystalline Zinc Oxide Photoanode Modified with CdO in Photoelectrocatalytic Degradation of Alcohols

Thin-film nanocrystalline zinc oxide electrodes were fabricated by electrochemical deposition of ZnO on FTO-coated glass slides. ZnO electrodes were promoted by CdO coating on top of ZnO in amounts corresponding to 0.8, 0.1, and 0.05 C cm−2 in electric units. Modification of ZnO by a small amount of CdO, corresponding to 0.05 C cm−2, shifts the photoactivity of the composite photoanode into the visible part of the solar spectrum. It is shown that the ZnO/(0.05C)CdO/FTO electrode demonstrates high efficiency in photoelectrochemical degradation of methanol, ethylene glycol, and glycerol when irradiated by a simulated sunlight. According to intensity-modulated photocurrent spectroscopy (IMPS), the effect is due to suppression of the electron–hole pairs recombination and increase in the rate of photo-induced charge transfer. Therefore, thin-film photoanodes based on zinc oxide modified by CdO can be used for photoelectrochemical degradation of byproducts of biofuel production glycerol, and of other alcohols.

Thorn-like morphology of TiO2 hierarchical structures for efficient dye-sensitized solar cell application

The efficiency of Dye-sensitized solar cells (DSSCs) can be improved through the employment of one-dimensional TiO2 nanostructured thin film photoanode materials. Herein, we have synthesized a 1D thorn-like nanostructure by the hydrothermal method as a photoanode in the DSSCs. The influence of the reaction time on the morphological, structural, and optical properties of the TiO2 nanostructures was studied. Field emission scanning electron microscopy (FE-SEM) showed the formation of nanothorn - like structures with an average length of 12 µm in 12 h reaction time, whereas a growth time of 18 h, micro flower-like structures were obtained. The dye-sensitized solar cell was fabricated with the two different prepared morphologies and the efficiency was found to be 0.51% and 1.2% for TiO2 samples prepared at 12 and 18 h.

Comprehensive evaluation of copper vanadate (α-CuV2O6) for use as a photoanode material for photoelectrochemical water splitting

This study is an initial account of solution-based spray pyrolysis-produced n-type copper vanadate (CuV2O6) thin film photoanodes. CuV2O6 photoelectrodes have been tested for their ability to oxidize water in aqueous (pH 6.8) solutions using photoelectrochemical (PEC) tests. The band edge positions, band gap energy, photocurrent generation, flat band potential, chemical make-up, chemical stability, charge carrier transit, and O2 production faradic efficiency are a few of the physical and photophysical features measured and described. According to the findings, CuV2O6 possesses a satisfactory bandgap of 1.9 eV and appropriate band locations that allow for the use of visible light for overall solar water splitting. Under AM1.5 simulated sunlight, the maximum photocurrent density recorded is 0.18 mA cm− 2 at 1.23 VRHE with Na2SO3 acting as a hole scavenger. As evidenced by film shape, surface compositions before and after the PEC measurements, and outstanding structural and compositional stability throughout the oxygen evolution reaction (OER), the CuV2O6 photoelectrodes performed well. CuV2O6 photoanodes also exhibit almost a unit faradic efficiency for the oxidation of water. The overall photoelectrochemical efficiency, however, is constrained by the photogenerated charge carriers' weak mobility (∼8 ×10−3 cm2 V−1 s−1), short lifetime (∼20 ns), and limited hole diffusion length (∼20.4 nm), according to time-resolved microwave conductivity (TRMC) tests. Based on the current findings, this study offers new insight into building enhanced high-quality CuV2O6 photoanodes by methodically clarifying numerous important physical and photoelectrochemical characteristics for the photooxidation of water.

Unveiling the Synchronized Effect of Bulk and Surface Dual Modification of In Situ Nb-Doping and Microwave-Assisted Co(OH)x Cocatalyst for Boosting Photoelectrochemical Water Splitting of Fe2O3 Photoanodes

Herein, in order to improve the conductivity and slack water oxidation kinetics of the hematite (α-Fe2O3) photoanode, we propose the Nb-doped and Co(OH)x cocatalyst-deposited α-Fe2O3 thin film photoanode (Nb-HT/Co(OH)x) via in situ diluted hydrothermal and microwave-assisted methods. The as-prepared Nb-HT/Co(OH)x thin-film photoanode exhibited a photocurrent density of 1.78 mA cm–2 at 1.23 V versus a reversible hydrogen electrode (RHE), which is 1.7-fold higher than that of the Bare-Fe2O3 photoanode. The dual effect of Nb-doping and Co(OH)x deposition markedly improved the PEC performance through enhancing the charge carrier mobility and donor density in hematite, as well as accelerating the interfacial charge transfer kinetics at the electrode/electrolyte interface of the α-Fe2O3 thin film photoanode. The Nb-HT/Co(OH)x photoanode displayed a high charge separation efficiency of 90% (at 1.23 VRHE) and excellent stability over a 10 h period without any decrease. Detailed electrochemical analyses using electrochemical impedance spectroscopy (EIS), open-circuit potential (OCP), and accumulated charge density techniques disclosed the charge separation and transfer processes. This strategy of bulk and surface modification highlights a new approach to constructing a stable photoanode for sustainable solar energy conversion.

Photoelectrocatalytic Degradation of Methylene Blue on Electrodeposited Bismuth Ferrite Perovskite Films.

Electrodeposited bismuth ferrite (BiFeO3) thin films on fluorine-doped tin oxide (FTO) substrate were employed as photoanodes in the photoelectrocatalytic degradation of methylene blue. The BiFeO3 thin films electrodeposited for 300 s, 600 s, 1200 s, 1800 s and 3600 s were characterised with XRD, field emission scanning electron microscopy (FESEM) and UV-vis diffuse reflectance spectroscopy. SEM images displayed different morphology at different electrodeposition times which affects the photoelectrocatalytic (PEC) performances. The FESEM cross-sectional area was used to measure the thickness of the film. The optical properties showed that the band gaps of the photoanodes were increasing as the electrodeposition time increased. The photocurrent response obtained showed that all thin film photoanodes responded to visible light and lower charge transfer resistance (from electrochemical impedance spectroscopy studies) was observed with photoanodes electrodeposited at a shorter time compared to those at a longer time. The PEC application of the photoanode for the removal of methylene blue (MB) dye in water showed that the percentage degradation decreased with an increase in electrodeposition time with removal rates of 97.6% and 70% observed in 300 s and 3600 s electrodeposition time, respectively. The extent of mineralisation was measured by total organic carbon and reusability studies were carried out. Control experiments such as adsorption, photolysis, photocatalysis and electrocatalysis processes were also investigated in comparison with PEC. The electrodeposition approach with citric acid exhibited improved electrode stability while mitigating the problem of catalyst leaching or peeling off during the PEC process.

Mesoporous CuFe2 O4 Photoanodes for Solar Water Oxidation: Impact of Surface Morphology on the Photoelectrochemical Properties.

Metal oxide-based photoelectrodes for solar water splitting often utilize nanostructures to increase the solid-liquid interface area. This reduces charge transport distances and increases the photocurrent for materials with short minority charge carrier diffusion lengths. While the merits of nanostructuring are well established, the effect of surface order on the photocurrent and carrier recombination has not yet received much attention in the literature. To evaluate the impact of pore ordering on the photoelectrochemical properties, mesoporous CuFe2 O4 (CFO) thin film photoanodes were prepared by dip-coating and soft-templating. Here, the pore order and geometry can be controlled by addition of copolymer surfactants poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (Pluronic® F-127), polyisobutylene-block-poly(ethylene oxide) (PIB-PEO) and poly(ethylene-co-butylene)-block-poly(ethylene oxide) (Kraton liquid™-PEO, KLE). The non-ordered CFO showed the highest photocurrent density of 0.2 mA/cm2 at 1.3 V vs. RHE for sulfite oxidation, but the least photocurrent density for water oxidation. Conversely, the ordered CFO presented the best photoelectrochemical water oxidation performance. These differences can be understood on the basis of the high surface area, which promotes hole transfer to sulfite (a fast hole acceptor), but retards oxidation of water (a slow hole acceptor) due to electron-hole recombination at the defective surface. This interpretation is confirmed by intensity-modulated photocurrent (IMPS) and vibrating Kelvin probe surface photovoltage spectroscopy (VKP-SPS). The lowest surface recombination rate was observed for the ordered KLE-based mesoporous CFO, which retains spherical pore shapes at the surface resulting in fewer surface defects. Overall, this work shows that the photoelectrochemical energy conversion efficiency of copper ferrite thin films is not just controlled by the surface area, but also by surface order.

Influence of solvent on accelerating deposition time of α-Fe2O3 photoanode via AACVD

The optical and photoelectrochemical (PEC) properties of semiconductors can be manipulated by varying the deposition time and the solvent used. In this work, the study investigates the influence of organic solvent (methanol and ethanol) on accelerating deposition time for the efficient optical and photoelectrochemical performance of the fabricated α-Fe2O3 thin film photoanode below 10 minutes. The α-Fe2O3 film was fabricated via aerosol-assisted chemical vapor deposition (AACVD). The study discovered that the solvent with high polarity enhanced the crystal growth direction of α-Fe2O3 on the (110) orientation. The UV-vis showed that all deposited α-Fe2O3 films exhibit the absorption band in the visible-light region with the estimated energy bandgap of 2.10 eV. Furthermore, the PEC performance exhibited good photoanodic responses with excellent charge transfer behavior and photostability. These findings show that the choice of solvent could influence the rapid deposition time, thus, would be reliable to accelerate the fabrication process of photoelectrochemical water-splitting photoanode.

Pristine GaFeO3 Photoanodes with Surface Charge Transfer Efficiency of Almost Unity at 1.23V for Photoelectrochemical Water Splitting.

Oxide-based photoelectrodes commonly generate deep trap states associated with various intrinsic defects such as vacancies, antisites, and dislocations, limiting their photoelectrochemical properties. Herein, it is reported that rhombohedral GaFeO3 (GFO) thin-film photoanodes exhibit defect-inactive features, which manifest themselves by negligible trap-states-associated charge recombination losses during photoelectrochemical water splitting. Unlike conventional defect-tolerant semiconductors, the origin of the defect-inactivity in GFO is the strongly preferred antisite formation, suppressing the generation of other defects that act as deep traps. In addition, defect-inactive GFO films possess really appropriate oxygen vacancy concentration for the oxygen evolution reaction (OER). As a result, the as-prepared GFO films achieve the surface charge transfer efficiency (ηsurface ) of 95.1% for photoelectrochemical water splitting at 1.23V versus RHE without any further modification, which is the highest ηsurface reported of any pristine inorganic photoanodes. The onset potential toward the OER remarkably coincides with the flat band potential of 0.43V versus RHE. This work not only demonstrates a new benchmark for the surface charge transfer yields of pristine metal oxides for solar water splitting but also enriches the arguments for defect tolerance and highlights the importance of rational tuning of oxygen vacancies.

Synergistic effect of Nd doping and plasmonic Au nanoparticles on BiFeO3thin film photoanodes for enhancing photoelectrochemical performance

The synergistic effect of Au NPs and Nd doping could improve the light utilization, promote the separation of photogenerated carriers and inhibit the recombination of photogenerated carriers, thus greatly improving the PEC performance of BFO.

Decoupling light absorption and carrier transport via heterogeneous doping in Ta3N5 thin film photoanode

The trade-off between light absorption and carrier transport in semiconductor thin film photoelectrodes is a major limiting factor of their solar-to-hydrogen efficiency for photoelectrochemical water splitting. Herein, we develop a heterogeneous doping strategy that combines surface doping with bulk gradient doping to decouple light absorption and carrier transport in a thin film photoelectrode. Taking La and Mg doped Ta3N5 thin film photoanode as an example, enhanced light absorption is achieved by surface La doping through alleviating anisotropic optical absorption, while efficient carrier transport in the bulk is maintained by the gradient band structure induced by gradient Mg doping. Moreover, the homojunction formed between the La-doped layer and the gradient Mg-doped layer further promotes charge separation. As a result, the heterogeneously doped photoanode yields a half-cell solar-to-hydrogen conversion efficiency of 4.07%, which establishes Ta3N5 as a leading performer among visible‐light‐responsive photoanodes. The heterogeneous doping strategy could be extended to other semiconductor thin film light absorbers to break performance trade-offs by decoupling light absorption and carrier transport.