Photoelectrocatalytic Properties Research Articles

Green synthesis of lead oxide nanoparticles for photo-electrocatalytic and antimicrobial applications.

Synthesis of nanoparticles (NPs) for many different uses requires the development of environmentally friendly synthesis protocols. In this article, we present a simple and environmentally friendly method to synthesize lead oxide (PbO) NPs from the plant material of the Mangifera indica. Analytical techniques such as spectroscopy, X-ray diffraction, and microscopy were used to characterize the synthesized PbO NPs, and their photo-electrocatalytic and antifungal properties were also evaluated. H2O2 was used to investigate the efficacy of removing methylene blue dye. At a range of pH values, H2O2 was used to study the role of hydroxyl radicals in the breakdown of methylene blue dye. Methylene blue dyes are more easily eliminated due to increased generation of the *OH radical during removal. Dye degradation was also significantly affected by the aqueous medium's pH. Additionally, the electrocatalytic properties of the PbO NPs adapted electrode were studied in CH3COONa aqueous solution using cyclic voltammetry. Excellent electrocatalytic properties of the PbO NPs are shown by the unity of the anodic and cathodic peaks of the modified electrode in comparison to the stranded electrode. Aspergillus flavus, Aspergillus niger, and Candida glabrata were some fungi tested with the PbO NPs. Against A. flavus (40%) and A. niger (50%), and C. glabrata (75%), the PbO NPs display an excellent inhibition zone. Finally, PbO NPs were used in antioxidant studies with the powerful antioxidant 2, 2 diphenyl-1-picrylhydrazyl (DPPH). This study presents a simple and environmentally friendly method for synthesizing PbO NPs with multiple uses, including photo-electrocatalytic and antimicrobial activity.

Investigation of Photoelectrocatalytic and Magnetic Properties of Sr2YbRu1-xTaxO6 (x = 0, 0.25, 0.5, 0.75, and 1).

We report the effect of substitution of Ru by Ta in Sr2YbRuO6 on its magnetic and photoelectrocatalytic properties. The powder X-ray diffraction data, was satisfactorily refined in the monoclinic space group, P21/n. The DC magnetization studies indicated that Sr2YbRuO6 shows antiferromagnetic interaction through Yb-O-Ru orbital ordering, with the highest Weiss temperature, among Sr2YbRu1-xTaxO6 (x = 0, 0.25, 0.5, and 0.75) which have values of -148, -125, -118, and -102 K, respectively. The difference in observed and theoretical magnetic moments was found to increase as x increases. It was also observed that with the increase of Ta concentration in Sr2YbRu1-xTaxO6, the band gap increased almost linearly, from 1.78(1) eV (x = 0) to 2.08(1) (x = 0.75), and thereafter a sharp increase 2.65(1) eV (x = 1) was observed, with the lowering of energy level of valence band, along with disruption in orbital ordering as x increases. The photoelectrocatalytic oxygen evolution reaction (OER) studies carried out on the series yield a maximum photocurrent density of 17 μA/cm2 and photoresponse current of 5.5 μA/cm2 at 0.8 V at an onset potential at 0.29 V vs Ag/AgCl for Sr2YbRuO6. The XPS analysis showed Ta and Ru to be in +5/+4 oxidation states, with the highest concentration of Ru4+ ion observed for Sr2YbRuO6. The presence of oxygen vacancies was confirmed by XPS as well as EPR studies.

Modulating Oxygen Vacancies in Lead Chromate forPhotoelectrocatalytic Water Splitting.

Although modulating oxygen vacancies in semiconductors has attracted broad interest in photocatalysis and photoelectrocatalysis, identifying the intrinsic roles of oxygen vacancies on photoelectrocatalytic properties is often elusive. In this work, the oxygen vacancies in a typical semiconductor lead chromate (PbCrO4 ) are regulated via controlling the oxygen chemical potentials of O-poor and O-rich post-annealing atmospheres. Oxygen vacancies identified in PbCrO4 can introduce electronically shallow energy levels and deep energy levels owing to the symmetry difference of oxygen atoms in the structure. A higher population of deep energy levels created under O-poor atmosphere induces the formation of more surface trapped states, resulting in a higher photovoltage for charge separation. Meanwhile, the existence of surface trapped states can significantly improve the charge injection efficiency of the PbCrO4 photoanode and enhance the water oxidation activity. By modulating oxygen vacancies in the PbCrO4 photoanode, a photocurrent density of 3.43mA cm-2 at 1.23V vs reversible hydrogen electrode (RHE) under simulated AM1.5G is acheived. Further passivation of surface trapped states and introducing the water oxidation cocatalyst CoPi lead to a record applied bias photon-to-current efficiency (ABPE) of 1.12%. This work provides a guide to understand the mechanism of oxygen vacancies in oxide-based semiconductor photocatalysis and photoelectrocatalysis.

Photocatalytic properties of molybdenum oxide photoelectrode synthesized by spray pyrolysis method

The present work reports the photoelectrocatalytic properties of pyrolyzed molybdenum oxide thin film. Microstructural analysis revealed clustered nanoaggregates. Structural analysis showed a polycrystalline $$\alpha$$ -MoO3 phase. The crystallite size, dislocation density, microstrain, and stacking faults were found to be 41.27 nm, 5.87 × 10−4 lines/cm2, 8.41 × 10−4 and 1.78, respectively. The optical bandgap was found to be 3.20 eV. Linear sweep voltammetry measurement in 1 M KOH electrolyte revealed a significant photocurrent density of 992.39 μA/cm2 at a bias of 1.2 V versus Ag/AgCl (1.4 V vs. RHE). The reasonable performance of the device suggests that the rarely deployed spray pyrolysis method is promising for preparing photoactive $$\alpha$$ -MoO3 films for photoelectrochemical measurement.

Combining the bioelectricity generation with Photo-Electrocatalytic reduction of CO2 for pollutants degradation and ethanol generation

Under this investigation, a p-n heterojunction nanocomposite (CuS/MgFe2O4) was synthesized using a simplified hydrothermal technique. According to the results of UV–vis diffuse reflectance spectroscopy (DRS) research, the creation of a p-n heterojunction structure lowered the band-gap value and improved the optical characteristics of the synthesized CuS/MgFe2O4 nanocomposite in contrast to CuS and MgFe2O4 nanoparticles. To investigate the electrocatalytic and photo-electrocatalytic properties of nanoparticles in the CO2 reduction reaction, first, the synthesized catalysts were immobilized by the electrophoretic deposition method (EPD) on a graphite electrode, and then various electrochemical techniques such as cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) were performed in the phosphate electrolyte (0.1 M, pH = 8) saturated with CO2 gas in the presence and absence of light. As a consequence, CuS/MgFe2O4/Graphite displayed a 2.2 and 1.3-fold increase in cathodic current density under light illumination compared to MgFe2O4/Graphite and CuS/Graphite, respectively. Using CuS/Graphite, MgFe2O4/Graphite, and CuS/MgFe2O4/Graphite as photocathodes in a two-chamber microbial fuel cell (MFC) caused a 13, 29, and 45 times increase, respectively, in the maximum power density compared to unmodified graphite. Gas chromatography-mass spectrometry (GC–MS) analysis revealed the presence of ethanol as the only detected CO2 conversion product, with a Faradic efficiency of about 35 %.

Tailoring the deposition of MoSe2 on TiO2 nanorods arrays via radiofrequency magnetron sputtering for enhanced photoelectrochemical water splitting

MoSe2/1 D TiO2 nanorods (NRs) heterojunction assembly was systematically fabricated, and its photoelectrocatalytic properties were investigated. The fabrication process involves the growth of 1D TiO2 NRs arrays on FTO substrates using hydrothermal synthesis followed by the deposition of MoSe2 nanosheets on the TiO2 NRs using radiofrequency magnetron sputtering (RF magnetron sputtering). The photoelectrochemical properties of the heterojunction were explored and optimized as a function of the thickness of the MoSe2 layer, which was controlled by the sputtering time. The MoSe2 grows perpendicularly on TiO2 NRs in a 2D layered structure, maximizing the exposed active edges, an essential aspect that permits maximum exploitation of deposited MoSe2.Compared to pure TiO2 NRs, the heterojunction nanostructured assembly displayed excellent spectral and photoelectrochemical properties, including more surface oxygen vacancies, enhanced visible-light absorption, higher photocurrent response, and decreased charge transfer resistance. In particular, the sample synthesized by sputtering of MoSe2 for 90 s, i.e., MoSe2@TiO2-90 s, depicted the highest current density (1.86 mA cm−2 at 0.5 V vs. Ag/AgCl) compared to other samples.The excellent photoelectrochemical activity of the heterojunction stemmed from the synergy between tailored loading of MoSe2 nanosheets and the 1D structure of TiO2 NRs, which afford a high surface/volume ratio, effective charge separation, fast electron transfer, and easy accessibility to the MoSe2 active edges. These factors boost the catalytic activity.

Application of Co3O4 in Photoelectrocatalytic Treatment of Wastewater Polluted with Organic Compounds: A Review

The negative effects of refractory organic substances in water on the environment and life have aroused worldwide attention. The efficiency of using photoelectrocatalysis (PEC) to degrade refractory organic pollutants depends to a large extent on the properties of the photoanode semiconductor. Therefore, the selection of a satisfactory photoanode semiconductor material to promote the production of intermediate reactive species (hydroxyl radicals and superoxide radicals) has become a key issue in improving the efficiency of PEC. Among the available catalysts, transition metal oxides have received a lot of attention in recent years due to their low price and significant advantages. Due to its outstanding photoelectrocatalytic properties, Co3O4 has emerged as a candidate to serve as a photoelectrocatalyst specifically for the oxidation of water with oxygen in these materials. This paper summarizes in detail the recent advances in Co3O4 materials for PEC, both pure Co3O4 and Co3O4-based composites. In addition, this review discusses the impact of strategies on the performance of photoelectrocatalysts, such as synthesis methods, crystal surface structures, and composites. Finally, this review concludes with a presentation of the challenges and workable solutions for Co3O4-based materials in PEC, along with a discussion of their potential for future research.

Enhancing the photo-electrocatalytic properties of g-C3N4 by boron doping and ZIF-8 hybridization

Enhancing the photo-electrocatalytic properties of g-C3N4 by boron doping and ZIF-8 hybridization

Ionic liquids and nanotechnology: Synthesis of WO3 nanostructures by anodization as photoelectrocatalysts

Two ionic liquids, [BMIM][BF4] and [EMIM][BF4], have been used for the first time to synthesize ordered and well-defined WO3 nanoplates by electrochemical anodization. Different amounts of these ionic liquids have been added to the electrolytes and their influence on the morphological, structural and photoelectrocatalytic properties of the WO3 nanoplates has been extensively studied. The resulted nanostructures, especially those synthesized in the presence of 5%–10% ionic liquids, showed excellent photoelectrocatalytic performances under irradiation, due to their better morphology, size and arrangement. These results confirm the potentiality of ionic liquids, such as [BMIM][BF4] and [EMIM][BF4], in the synthesis by anodization of high-efficiency photoelectrocatalysts, which could be used in the energy and environmental fields.

Template-Assisted SnO2: Synthesis, Composition, and Photoelectrocatalytical Properties

A series of tin oxides were synthesized with polystyrene microspheres (250 nm) as the template. It was shown that an increase in the template content led to increasing specific pore volume and to the formation of bimodal pore structure with pores of 9 and 70 nm in diameter. Addition of cetyltrimethylammonium bromide (CTAB) during synthesis led to the formation of friable structures (SEM data), to an increase in the average pore diameter from 19 to 111 nm, and to the formation of macropores of 80–400 nm in size. All materials had similar surface properties and cassiterite structure with 5.9–10.8 nm coherent scattering region (XRD data). Flat-band potentials of the samples were determined and their photoelectrocatalytic properties to oxidation of water and methanol were studied in the potential range of 0.4–1.6 V RHE. It was shown that the sample obtained using CTAB was characterized by lower flat-band potential value, but appeared significantly higher photocurrent in methanol oxidation, which resulted from enhanced macro-meso-porous structure to facilitate methanol pore diffusion.

Fabrication of Eco-friendly Hybrid Active Imidazole based Ionic Liquid Embedded Cadmium Oxide-TiO2 Catalyst for Photoelectrocatalytic and Hydrophobic Properties

In this work, a new and straightforward method for the synthesis of 1-hexyl-3-methyl-2-(2-oxo-ethyl)- 3H-imidazol-1-ium bromide (HMIB) embedded on CdO-TiO2 (HMIB-CT) hybrid material is reported. The efficiency of the catalytically active material HMIB-CT with nanostructures is entirely depend on the preparation method. The X-ray diffraction patterns revealed that the anatase phase of titanium dioxide results in the formation of well-crystallized CdO and ionic liquid. The optical absorbance spectra demonstrated that the energy gap is diminished from 2.80 to 2.37 eV, which happens due to the presence of ionic liquids. The HR-TEM study shows that the particles are present in spherical shape, while some particles are rod structures with small amount of agglomeration found in imidazole based ionic liquid embedded CdO-TiO2 nanoparticles. The photoluminescence emission results also indicated that ionic liquids efficiently supported and blocked the recombination of charge carriers. A complete demineralization of an organic dye (Trypan blue) under natural sun beam irradiation required for the photocatalytic activity is also accomplished. Moreover, the prepared ionic liquid supported CdO-TiO2 hybrid material shows better electrocatalytic activity upon methanol oxidation (4.89 mA) and super hydrophobic nature by contact angle measurement (112.2º).

Hydrothermal synthesis of Z-scheme Bi2WO6/Bi2MoO6 heterojunctions for the enhanced photoelectrocatalytic performance of TiO2 NTs: Structure, activity and mechanism approach

In this paper, the direct Z-scheme Bi2WO6-Bi2MoO6 heterojunctions were constructed by the simple hydrothermal deposition on TiO2 nanotube arrays (TiO2 NTs). The results revealed Bi2WO6/Bi2MoO6 heterojunctions dramatically enhanced the solar absorption and slowed the electron recombination, which improved the photoelectrocatalytic pollutant removal property, and •OH and •O2 radicals were the decisive active species. Moreover, the TiO2 NTs/Bi2WO6-Bi2MoO6 photoelectrode exhibited excellent photoelectric conversion and photoelectrocatalytic H2 evolution properties, much higher than the data of TiO2 NTs/Bi2WO6 and TiO2 NTs/Bi2MoO6 photoelectrodes. The visible light photoelectrocatalytic H2 evolution rate of TiO2 NTs/Bi2WO6-Bi2MoO6 photoelectrode was 38.03 μmol·h−1·cm−2, and it still showed high photocatalytic activity after several experimental cycles. The outstanding photocatalytic activity of TiO2 NTs/Bi2WO6-Bi2MoO6 sample provides a referential template of the Z-scheme heterojunction construction for the application in photocatalytic pollutant removal and H2 evolution.

Electrically conductive TiO2/CB/PVDF membranes for synchronous cross-flow filtration and solar photoelectrocatalysis

Combining photocatalysis (PC) and membrane filtration (MF) has emerged as an attractive technology for water purification, however, the water purification efficiency and membrane fouling are still challenging. Herein, we report a novel photoelectrocatalytic (PEC) membrane mediated by a ternary polyvinylidene fluoride (PVDF)-carbon black (CB)–TiO2 composite conductive membrane synthesized by a phase inversion method assisted by the mixed surfactants of polyvinylpyrrolidone (PVP) and sodium dodecyl sulfate (SDS). The resultant electrically conductive TiO2/CB/PVDF membrane features a homogeneous surface with obvious pore size of 20–150 nm, a thickness ∼116 μm, and an average resistivity as low as ∼3.165 Ω∙m. The cooperation of PVP and SDS surfactants dramatically improves the organic-inorganic interactions and thus eventually enhances the porosity, stability of porous structure, mechanical stability, and conductivity and electrochemical properties of the hybrid membrane. Upon the solvent evaperation of the wellblended casting solution and the phase inversion, TiO2/CB preferentially exist on the surface of PVDF membrane, enabling the efficient PEC degradation of organic pollutants. The synergistic coupling of TiO2 and CB in PVDF membrane results in efficient PEC properties with bi-functional membrane antifouling and enhanced water purification in azo dyes decolorization under the stationary mode and in our lab-made continuous cross-flow PEC system, superior to those by photocatalysis and electrocatalysis. The developed synchronous MF and PEC system mediated by the conductive TiO2/CB/PVDF membrane proves to a feasible route to improving the self-cleaning properties of the polymer membrane while simultaneously increasing the water decontaminating efficiency.

Effect of the conductive substrate on the photoelectrocatalytic properties of hematite for water splitting

In this paper, hematite photoanodes were prepared on F-doped SnO2 glass (FTO), polystyrene microspheres (PS), a three-dimensional conductive substrate prepared from a monolayer PS template (MM-TCS) and a bilayer PS template (B-TCS) by a hydrothermal method, and the effect of the different substrates on the photoelectrocatalytic (PEC) performance of hematite was investigated. At 1.23 V (vs RHE), the hematite photoanode prepared on B-TCS (B-TCS-hematite) has the optimal photocurrent response of 1.16 mA cm−2, which is 4.6 times that of the hematite photoanode prepared on FTO (FTO-hematite). The improved PEC performance of the B-TCS-hematite sample is mainly due to the thicker and more connected B-TCS layers, the high ratio of (104)/(110), the morphology of nanocoral rods with larger gaps and the increased light absorption, which significantly improve the bulk charge separation efficiency and surface charge injection efficiency. In this work, the effects of conductive substrates on the photoelectrocatalytic water of hematite were investigated by scanning electron microscopy (SEM), UV–vis spectroscopy, X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), and photoelectrical measurements.

Understanding the Photoelectrochemical Properties of Theoretically Predicted Water‐Splitting Catalysts for Effective Materials Discovery

AbstractData‐intensive discovery of water‐splitting catalysts can accelerate the development of sustainable energy technologies, such as the photocatalytic and/or electrocatalytic production of renewable hydrogen fuel. Through computational screening, 13 materials were recently predicted as potential water‐splitting photocatalysts: Cu3NbS4, CuYS2, SrCu2O2, CuGaO2, Na3BiO4, Sr2PbO4, LaCuOS, LaCuOSe, Na2TeO4, La4O4Se3, Cu2WS4, BaCu2O2, and CuAlO2. Herein, these materials are synthesized, their bandgaps and band alignments are experimentally determined, and their photoelectrocatalytic hydrogen evolution properties are assessed. Using cyclic voltammetry and chopped illumination experiments, 9 of the 13 materials are experimentally found to have bandgaps and band alignments that straddle the potentials required for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), as computationally predicted. During photocatalytic testing, 12 of the materials yield a measurable photocurrent. However, only three are found to be active for the HER, with Cu3NbS4, CuYS2, and Cu2WS4 producing H2 in amounts comparable to bare TiO2; a benchmark photocatalyst. This study provides experimental validation of computational bandgap and band alignment predictions while also successfully identifying active photocatalysts.

Plasmon-induced hole-depletion layer on p-n heterojunction for highly efficient photoelectrochemical water splitting

The photoelectrocatalytic (PEC) water splitting efficiency of semiconductor photoelectrodes is mainly limited by the effective separation and transfer of photogenerated charges. Zinc indium sulfide-cuprous oxide (ZnIn2S4-Cu2O) p-n heterojunction is constructed to enhance the PEC properties of ZnIn2S4. The nickel hydroxide iron oxide (NiFeOOH) layer on the surface of the heterojunction can be used as a hole depletion layer under the induction of plasmon resonance of the most surface silver (Ag) (the holes transferred from Cu2O valence band to NiFeOOH layer can be excited by Ag to produce hot electron consumption, which makes the last remaining hot holes participate in the water oxidation reaction) to further promote the carrier separation and transfer. The results exhibit that ZnIn2S4/Cu2O/NiFeOOH/Ag photoelectrode with dramatically enhanced photocurrent density of 1.22 mA/cm2 at 1.23 V versus the reversible hydrogen electrode (VRHE), which is 9.4 times higher than the pure ZnIn2S4. This work provides a promising concept to design photoelectrodes efficiently in PEC water splitting.

Hydrothermal modification of TiO2 nanotubes in water and alkali metal electrolytes (LiNO3, NaNO3, KNO3) – Direct evidence for photocatalytic activity enhancement

The influence of hydrothermal annealing (HA) of TiO2 nanotubes (TiO2-NTs) in various baths (H2O, LiNO3, NaNO3, KNO3 performed for 4 h, 24 h, 64 h), on their photocatalytic and photoelectrocatalytic properties, was studied. The use of electrolytes was to enable the monitoring of photoactivity changes as a result of the expected impact on the population of hydroxyl groups on the surface. The assumption turned out to be correct and it was proved that the presence of Li+, Na+ or K+ does not allow achieving the same increases in photoactivity as observed for water. Modified samples exhibit significantly decreased F, P and carbon containing species. The length of the HA annealing time considerably affected the geometry of the nanotubes: eliminated clusters, changing the tilting angle of nanotubes, the wall thickness and inter-nanotube distance. Morphology changes due to HA treatment were associated with the interference phenomenon recorded as maximum in the Vis range. HA treatment in water brings about the most photoactive and photoelectroactive material characterized with minor modification in the optical bandgap and position of the flat bad potential. The optical energy bandgap values for electrodes containing alkali metals were reduced (up to 2.72 eV) and flat-band potential was shifted towards the anodic direction (up to 0.25 V disparity). However, increased activity as photocatalysts in the methylene blue degradation process and higher photocurrent generation was achieved for samples after modification in distilled water than in electrolytes, but these parameters are still better in comparison to unmodified titania nanotubes. Long-term treatment in water and electrolytes reduced threshold potentials for oxygen evolution reaction. The studies confirmed the effectiveness of the hydrothermal method for obtaining better photocatalytic parameters of TiO2-NTs and indicate that the presence of alkali metals is not favourable for maintaining high photocatalytic parameters.

Effect of W concentration in the organized Ti-W alloy oxide nanotubes array on the photoelectrocatalytic properties and its application in the removal of endocrine disruptors using real water matrix

To evaluate the tungsten content on the photoelectrocatalytic properties of self-organized nanotubes grown by anodization on Ti-xW (wt%) alloys, where x is 0.5, 2.5 or 5.0, this work investigated the phase transformation of TiO2, the tungsten oxidation states in the oxide layers and their photoelectrocatalytic performance in the degradation of estrone (E1) and 17α-ethinylestradiol (EE2). These films were employed in photocatalytic and photoelectrocatalytic removals of hormones from synthetic and real water matrices. In synthetic water, E1 and EE2 removals, reached efficiencies of 92% and 71%, respectively, after 2 min under UV–Vis photoelectrocatalysis using NT/Ti-5.0W as catalyst. About 30 times longer was needed to degrade 77% of both hormones from the real water matrix due to the presence of other high organic charge. The high performance of the NT/Ti-5.0W was associated with the combination of doping (W-doped TiO2) and WO3 (W6+) heterojunction. However, this electrode had its stability compromised under long degradation times, mainly under visible light, due to a WO3 leaching process. As for NT/Ti-0.5W, the substitutional W-doped TiO2 contributed to its greater stability and efficiency for a long time. The low performance of NT/Ti-2.5W was justified by high density of oxygen vacancy and unfavorable position of its adsorption bands.

Ni Foam Supported TiO2 Nanorod Arrays with CdS Branches: Type II and Z‐Scheme Mechanisms Coexisted Monolithic Catalyst Film for Improved Photocatalytic H2 Production

TiO2 has garnered a flourish of interest in the field of energy storage and energy conversion. Herein, a new generation of 3D Ni foam supported in situ grown 1D TiO2 nanoarray (Ni/TiO2) is successfully prepared, through an easy solution‐phase hydrothermal process, and then CdS nanorods branched Ni/TiO2 nanoarrays are fabricated (Ni/TiO2@CdS). Their formation parameters and growth mechanism are carefully studied. Both Ni/TiO2 and Ni/TiO2@CdS monolithic catalysts exhibit advantaged photocatalytic (PC) and photoelectrocatalytic (PEC) water splitting properties compared with that of most previously reported TiO2‐based film photocatalysts. Mechanism investigation reveals that both type II and Z‐scheme charge transport mechanisms coexist in Ni/TiO2@CdS sample, and an additional Z‐scheme charge transfer effect accelerates the photogenerated charge separation and transport efficiency. This study may open a new avenue for the utilization of TiO2‐based film catalysts in a broader field of energy and environmental catalysis areas.

Role of an Inert Electrode Support in Plasmonic Electrocatalysis

Direct loading of plasmonic nanostructures onto catalytically inert conductive support materials leads to the Schottky barrier-free architecture of the photocatalytic system. Such systems have recently attracted the attention of the research community as they permit collection of hot carriers independent of their energy when additional charge separation strategies are used. However, a systematic mechanistic investigation and description of the contribution of an inert conductive support to plasmonic electrocatalysis is missing. Herein, we systematically investigated the effect of the supporting electrode material on the observed photoinduced enhancement by comparing the photoelectrocatalytic properties of AuNPs supported on highly oriented pyrolytic graphite (HOPG) and indium tin oxide (ITO) electrodes using electrocatalytic benzyl alcohol (BnOH) oxidation as a model system. Upon illumination, only ∼(3 ± 1)% enhancement in catalytic current was recorded on the AuNP/ITO electrodes in contrast to ∼(42 ± 6)% enhancement on AuNP/HOPG electrodes. Our results showed that the local heating due to light absorption by the electrode material itself independent of localized surface plasmon effects is the primary source of the observed significant photoinduced enhancement on the HOPG electrodes in comparison to the ITO electrodes. Moreover, we demonstrated that an increased interfacial charge transfer at elevated temperatures and not faster reactant diffusion as suggested previously is the main source of the thermal enhancement. This work highlights the importance of the systematic evaluation of contributions of all parts, even if they are catalytically inert, to the light-induced facilitation of catalytic reactions in plasmonic systems.