Hematite Photoanodes Research Articles

In-situ synthesis of Fe phosphate layer on the porous hematite nanocube for efficient photoelectrochemical water splitting

Hematite (α-Fe2O3) is considered as an ideal photoanode material in photoelectrochemical (PEC) water splitting system due to its suitable band gap, excellent stability and abundant reserves. However, the actual PEC water oxidation performance of α-Fe2O3 is greatly limited by its severe charge recombination and sluggish water oxidation kinetics. Here, an in-situ generated Fe phosphate (Fe-Pi) coating strategy is applied on the surface of porous hematite nanocube (Fe2O3 NC) to realize PEC water oxidation effectively. The obtained Fe-Pi/Fe2O3 NC photoanode exhibits a remarkable PEC property with a photocurrent density of 2.7mAcm-2 at 1.23V vs. RHE, which was about 5.7-fold enlarged compared to the pristine nanorod-like hematite (Fe2O3 NR) photoanode. Detailed studies have shown that the porous Fe2O3 NC possesses an enhanced ability in light absorption and charge separation than the traditional Fe2O3 NR photoanode. In addition, the in-situ loading of Fe-Pi layer as a co-catalyst can not only effectively passivate the surface trapping states of Fe2O3 NC and suppress interfacial charge recombination, but also quickly extract the holes to participate in the water oxidation reaction. Our study suggests that the further surface modification based on morphological engineering is an effective strategy to improve the PEC performance of hematite.

Integration of element codoping and electron-donor functional groups into metal–organic framework to improve photoelectrochemical water oxidation of hematite photoanode

Integration of element codoping and electron-donor functional groups into metal–organic framework to improve photoelectrochemical water oxidation of hematite photoanode

Enhanced PEC generation of hydrogen from seawater driven by efficient and stable Ti-Fe2O3 photoanode

Incorporation of Ti4+ ions into the hematite (α-Fe2O3) photoanodes has garnered significant consideration for the photoelectrochemical water splitting process since it improves the charge transport and optical properties of pristine hematite material. Herein, we have approached a facile route to fabricate the thin films of Ti-Fe2O3 by spray pyrolysis treatment. The Ti-Fe2O3 photocurrent density delivers 1.34 mA/cm2 at 1.23 V RHE in an alkaline seawater environment, showing its excellent performance for photoelectrochemical water- splitting applications. Moreover, it offers outstanding stability in seawater (0.5 M NaCl + 1 M KOH) at applied 1.23 V for 20 h and produces 21.79 µmol/cm2.h of hydrogen. Hence, it will hold a tremendously promising electrode within this area for efficient solar hydrogen generation.

The role of titanium at the interface of hematite photoanode in multisite mechanism: Reactive site or cocatalyst site?

The role of titanium at the interface of hematite photoanode in multisite mechanism: Reactive site or cocatalyst site?

Constructing Metal-Organic Framework Films with Adjustable Electronic Properties on Hematite Photoanode for Boosting Photogenerated Carrier Transport.

Hematite (α-Fe2O3) has become a research hotspot in the field of photoelectrochemical water splitting (PEC-WS), but the low photogenerated carrier separation efficiency limits further application. The electronic structure regulation, such as element doping and organic functional groups with different electrical properties, is applied to alleviate the problems of poor electrical conductivity, interface defects, and band mismatch. Herein, α-Fe2O3 photoanodes are modified to regulate their electric structures and improve photogenerated carrier transport by the bimetallic metal-organic frameworks (MOFs), which are constructed with Fe/Ni and terephthalate (BDC) with 2-substitution of different organic functional groups (─H, ─Br, ─NO2 and ─NH2). The α-Fe2O3 photoanode loaded with FeNi-NH2BDC MOF catalyst exhibits the optimal photocurrent density (2mAcm-2) at 1.23VRHE, which is 2.33 times that of the pure α-Fe2O3 photoanode. The detailed PEC analyses demonstrate that the bimetallic synergistic effect between Fe and Ni can improve the conductivity and inhibit the photogenerated carrier recombination of α-Fe2O3 photoanodes. The ─NH2 group as an electron-donor group can effectively regulate the electron distribution and band structure of α-Fe2O3 photoanodes to prolong the lifetime of photogenerated holes, which facilitates photogenerated carrier transport and further enhances the PEC-WS performance of α-Fe2O3 photoanode.

High‐Performance Hematite Photoanodes for Unassisted Recharging of Solar Redox Flow Battery

Solar redox flow batteries (SRFB) have attracted increasing interest for simultaneous capture and storage of solar energy by integrating a photoelectrochemical cell with a redox flow battery. Herein, a scalable, nanostructured α‐Fe2O3 photoanode exhibiting a high photovoltage of 0.68 V in a fully integrated Na4Fe(CN)6/AQDS SRFB is demonstrated. Thanks to its optimal band alignment, it uniquely enables stable, unassisted photocharging of the SRFB up to a state‐of‐charge (SOC) higher than 50%. Concurrently, its improved charge transfer results in a record unbiased photocurrent density of 0.22 mA cm−2, with a sixfold increase at zero SOC compared to α‐Fe2O3 film. Through an in‐depth optical and photoelectrochemical characterization of different α‐Fe2O3 morphologies, the impact of nanostructuring on charge transfer is quantified. Most interestingly, an increase in unbiased photocurrent is observed at 10% SOC (0.31 mA cm−2) and attributed to adsorption of ferricyanide, which enhances charge transfer. Importantly, it is demonstrated that the superior performance is retained after device scale‐up to 5.72 cm2. Overall, the demonstrated unassisted device is on par with previously reported dye‐sensitized solar cell‐assisted hematite‐based SRFBs. More broadly, this work contributes to the real‐world deployment of cost‐effective SRFBs based on Earth‐abundant materials.

Operando spectroelectrochemical insights into the selectivity difference of photoelectrocatalytic alcohol oxidation to aldehyde on hematite and titania

Operando spectroelectrochemical spectroscopy is employed to investigate the selectivity of ethanol oxidation on hematite and titania photoanodes. High selectivity of acetaldehyde formation from ethanol oxidation has been identified using the hematite photoanode, whilst modest selectivity and over-oxidation of acetaldehyde are observed using titania photoanodes. This difference in the acetaldehyde selectivity is correlated with the valence band potential. The valence band potential is also associated with the activation energy required for the over-oxidation of acetaldehyde. The activation energy of acetaldehyde oxidation by the photogenerated holes in hematite is 427 meV whilst only 45 meV is required for titania. Kinetic isotope effect shows that the rate-limiting step of ethanol oxidation on hematite and titania involves α-C–H bond breaking, and solvent molecules are important to assist the rehybridization of this α-C. The spectral analyses emphasize the importance of considering the band potential upon the selectivity of alcohol oxidation on a broad scope.

Boosting Acidic Water Oxidation on Hematite Photoanodes with Synergistic Effects of Ce‐Doped Co3O4 Nanoparticles

AbstractPhotoelectrochemical (PEC) water splitting is pivotal for addressing the clean and renewable energy demands. However, developing low‐cost, efficient, and robust non‐precious metal catalysts for the acidic oxygen evolution reaction (OER) remains a significant challenge. In this study, we introduced Ce to modulate the electronic structure of Co3O4, enhancing the stability of Co3O4 without compromising its activity. Ce‐doped Co3O4 nanoparticles were electrodeposited onto Ti‐doped hematite surfaces (Ce : Co3O4/Fe2O3), significantly enhancing the PEC performance for water splitting under acidic conditions. These catalysts achieved high photocurrent densities and exhibited prolonged stability. Functioning as p‐type semiconductors, the Ce : Co3O4 nanoparticles not only boosted light absorption but also formed a p‐n heterojunction with the Ti‐doped hematite. This heterojunction generated a built‐in electric field that facilitated the separation and transfer of photogenerated carriers, thereby improving charge separation efficiency. Additionally, these nanoparticles expanded the active surface area of hematite and served as a co‐catalyst, markedly accelerating the OER kinetics. The Ce : Co3O4/Fe2O3 photoanode achieved an impressive photocurrent density of 1.08 mA cm−2 at 1.23 VRHE in acidic media, demonstrating its enhanced activity and stability.

Acceleration of bulk and surface charger transfer dynamics via FePi cocatalyst-coated Ti/(Sb)-Fe2O3:Sb/(Ti)-Fe2O3 type-II homojunction photoanode for photoelectrochemical performance

Hematite (α-Fe2O3) possesses notable benefits in the field of photoelectrochemical (PEC) water splitting. However, the overall low efficiency of the separation and transfer of photogenerated charge carriers significantly hinders its further utilization. Although the occurrence of an internal electric field has the potential to significantly augment the efficiency of charge separation and transfer, there is a crucial need to broaden the scope of its successful application. This study explores a strategy for modifying the coupling between homojunction formation with gradient doping and cocatalyst modification on hematite to boost PEC performance. The developed type II Ti-doped/(Sb-codoped) Fe2O3:Sb-doped/(Ti-codoped) Fe2O3 (Ti/(Sb)-HT:Sb/(Ti)-HT) homojunction with a staggered band alignment accelerated the bulk charge separation via an intrinsic built-in electric field, while the bulk conductivity was improved using a gradient co-doping approach. Furthermore, the deposition of a FePi cocatalyst expedited the transfer of holes from the photoanode to the electrolyte by increasing the surface states, thereby hastening the water oxidation kinetics. The resulting Ti/(Sb)-HT:Sb/(Ti)-HT@FePi photoanode exhibited a 78.7% increase in photocurrent density compared to the bare Ti-Fe2O3 photoanode (0.94–1.68 mA/cm2 at 1.23 VRHE), accompanied by a charge transfer efficiency of 72.5%. Comprehensive photoelectrochemical investigations revealed that the homojunction and cocatalyst play a vital role in improving the dynamics of both the bulk and surface of the hematite photoanode, thereby facilitating efficient water oxidation. These findings offer a deeper insight into the function of homojunction photoanodes adorned with cocatalysts in the solar water-splitting process.

Subtraction Descriptors in Machine Learning for Optimizing the Cocatalyst Effect of Cobalt Phosphate on Hematite Photoanodes.

In the quest for sustainable energy solutions, the optimization of the photoelectrochemical (PEC) performance of hematite photoanodes through cocatalysts represents a promising avenue. This study introduces a novel machine learning approach, leveraging subtraction descriptors, to isolate and quantify the specific effects of cobalt phosphate (Co-Pi) as a cocatalyst on hematite's PEC performance. By integrating data from various analytical techniques, including photoelectrochemical impedance spectroscopy and ultraviolet-visible spectroscopy, with advanced machine learning models, we successfully predicted the PEC performance enhancement attributed to Co-Pi. The Gaussian process regression (GPR) model emerged as the most effective, revealing the critical influence of the interfacial resistance, bulk resistance, and interfacial capacitance on the PEC performance. These findings underscore the potential of cocatalysts in improving charge separation and extending charge carrier lifetimes, thereby boosting the efficiency of photocatalytic reactions. This study not only advances our understanding of the cocatalyst effect in photocatalytic systems but also demonstrates the power of machine learning in modifying complex materials and guiding the development of optimized photocatalytic materials. The implications of this research extend beyond hematite photoanodes, offering a generalizable framework for enhancing the photoelectrochemical properties of a wide range of material modifications such as cocatalyst deposition, doping, and passivation.

Advances in Functional Ceramics for Water Splitting: A Comprehensive Review

The global demand for sustainable energy sources has led to extensive research regarding (green) hydrogen production technologies, with water splitting emerging as a promising avenue. In the near future the calculated hydrogen demand is expected to be 2.3 Gt per year. For green hydrogen production, 1.5 ppm of Earth’s freshwater, or 30 ppb of saltwater, is required each year, which is less than that currently consumed by fossil fuel-based energy. Functional ceramics, known for their stability and tunable properties, have garnered attention in the field of water splitting. This review provides an in-depth analysis of recent advancements in functional ceramics for water splitting, addressing key mechanisms, challenges, and prospects. Theoretical aspects, including electronic structure and crystallography, are explored to understand the catalytic behavior of these materials. Hematite photoanodes, vital for solar-driven water splitting, are discussed alongside strategies to enhance their performance, such as heterojunction structures and cocatalyst integration. Compositionally complex perovskite oxides and high-entropy alloys/ceramics are investigated for their potential for use in solar thermochemical water splitting, highlighting innovative approaches and challenges. Further exploration encompasses inorganic materials like metal oxides, molybdates, and rare earth compounds, revealing their catalytic activity and potential for water-splitting applications. Despite progress, challenges persist, indicating the need for continued research in the fields of material design and synthesis to advance sustainable hydrogen production.

Enhanced Water Oxidation of Hematite Photoanodes via Localized n‐p Homojunctions Induced by Gradient Zn2+ Doping

AbstractConstructing an internal electric field (IEF) within the hematite (Fe2O3) photoanode for highly efficient water oxidation performance with facilitated charge transfer and separation remains still a significant challenge. Unlike the conventional approach of creating interfacial electric fields through heterojunction design by introducing another semiconductor, a novel strategy is proposed for engineering localized n‐p homojunctions on the surface of Fe2O3 photoanode using gradient Zn2+ doping strategy. By implementing this approach, the inherent n‐type characteristics of Fe2O3 can be transformed into p‐type, thereby facilitating the formation of an n‐p junction with robust IEF, which enables more efficient charge separation and transfer. Additionally, the gradient Zn2+ doping is accompanied by the generation of oxygen vacancies, which further improves the charge transfer efficiency and accelerates water oxidation kinetics. As expected, the photocurrent density of optimized Fe2O3 photoanode at 1.23 V versus reversible hydrogen electrode is ≈2.6‐fold that of Fe2O3. This work provides a novel perspective on the design of localized n‐p homojunction within photoanodes for achieving high solar energy conversion efficiency.

Unlocking the potential of hematite photoanodes in acidic electrolytes: Boosting performance with ultra‐small IrOx nanoparticles for efficient water splitting

AbstractPhotoelectrochemical (PEC) water splitting offers a promising route for harnessing solar energy to produce clean hydrogen fuel sustainably. A major hurdle has been boosting the performance of photoanode materials within acidic electrolytes—a critical aspect for advancing PEC technology. In response to this challenge, we report a method to augment the efficacy of hematite photoanodes under acidic conditions by anchoring IrOx nanoparticles, replete with hydroxyl groups, onto their surface. A remarkable and steady photocurrent density of 1.71 mA cm−2 at 1.23 V versus RHE was achieved, marking a significant leap in PEC efficiency of hematite in acidic media. The introduction of the IrOx layer notably expanded the electrochemically active surface area for more active sites, fostering improved charge separation and transfer. It also served as an effective hole capture layer, drawing photogenerated holes from hematite to facilitate swift migration to the active sites for the water oxidation process. This advancement has the potential to fully harness the capabilities of hematite photoanodes in acidic environments, thereby smoothing the path toward more effective and sustainable hydrogen production through PEC water splitting.

Combined Effect of Underlayer and Deposition Solution to Optimize the Alignment of Hematite Photoanodes.

This study investigates the optimization of hematite (α-Fe2O3) photoanodes for enhanced photoelectrochemical (PEC) performance and reproducibility, which are crucial for photocatalytic applications. Despite hematite's potential, hindered by inherent limitations, significant improvements were realized by introducing a titanium dioxide (TiO2) underlayer and ethanol-modified deposition. The influence of the deposition methods was understood by potential-dependent photoelectrochemical impedance spectroscopy analysis. The introduction of the TiO2 underlayer effectively increased the density of states, preferable for the electron transport in the bulk hematite, and the ethanol deposition on a TiO2 underlayer led to a stable surface state formation (S1 state) for the photoexcited hole transfer. This analysis illuminated the intricate interplay between electron transport in the bulk and photogenerated hole transfer at the solution interface, thereby facilitating smoother charge transfer. These findings underscore the viability of surface engineering and meticulous process optimization in addressing critical challenges in photocatalyst development.

Ge-Doped Hematite with FeCoNi-Bi as Cocatalyst for High-Performing Photoelectrochemical Water Splitting.

Hematite is a promising photoanode material for photoelectrochemical water-splitting technology. However, the low current density associated with the low conductivity, low charge carrier mobility, and poor oxygen evolution catalytic activity is a challenging issue for the material. In this study, the challenge is addressed by introducing Germanium (Ge) doping, coupled with the use of FeCoNi-Bi as a co-catalyst. Ge doping not only increases the conductivity and charge carrier concentration of the hematite photoanode, but also induces nanopores, thereby expanding its electrochemical reactive surface area to facilitate the oxygen evolution reaction. In the meantime, the FeCoNi-Bi cocatalyst electrodeposited onto the surface of Ge-doped hematite, improves the oxygen evolution reaction performance. As a result, the obtained photoanode achieves a photocurrent density of 2.31mAcm-2 at 1.23 VRHE, which is three times higher than that of hematite (0.72mAcm-2). Moreover, a new analytical method is introduced to scrutinize both the positive and negative effects of Ge doping and FeCoNi-Bi cocatalyst on the photoanode performance by decoupling the photoelectrochemical process steps. Overall, this study not only enhances the performance of hematite photoanodes but also guides their rational design and systematic assessment.

A facile route for decoration of hematite photoanodes by transition metal hydroxide co‐catalysts

AbstractEarth‐abundant α‐Fe2O3 (hematite) is a convincing photoanode for photoelectrochemical (PEC) water splitting; however, its intrinsic properties of inferior charge transfer and sluggish water oxidation kinetics limit its performance. Here, we report a straightforward decoration method for transition metal hydroxides to accelerate the oxygen evolution reaction (OER) of hematite photoanodes grown by electric field‐assisted liquid phase deposition (EA‐LPD). The investigations revealed that Co(OH)2 acts as a superior co‐catalyst compared with hydroxides of Mn, Fe, Co, Ni, and Zn. EA‐LPD‐grown hematite photoanode loaded with cobalt hydroxide exhibited an excellent PEC performance. A photocurrent density of 0.93 mA.cm−2 at 1.23 V versus reversible hydrogen electrode was achieved for the modified hematite, ∼3 times more than that of pristine hematite, and a cathodic shift of 100 mV for the onset potential was observed. The proposed simple and cost‐effective co‐catalyst loading strategy provides a high degree of freedom in the design of co‐catalysts with a complex chemical composition comprising transition metal oxyhydroxides and hydroxides on different photoanodes for more efficient charge carrier separation for the PEC applications.

Bulk and interface engineering with the combined addition of Na+ and E5+ (E = Nb5+, Ta5+) in the design of hematite photoanodes

In this letter, the synergistic effects of multiple element modification through a single polymeric precursor solution in hematite-based photoanodes using Na/Nb and Na/Ta as dopants are evaluated. Linear sweep voltammetry curves showed that the photoelectrochemical response was improved after Na/Nb (or Ta) addition. In both circumstances, an anodic shift (∼200 mV) in the onset potential was noticeable due to surface states created after Nb5+/Ta5+ segregation. The energetic loss caused by Nb (and Ta) segregation was partially restituted by NiFeOx addition due to the passivation of surface states, acting as recombination centers created by pentavalent modifiers. These combined modifications brought a three and four-fold increase for Na0.1HemNb1.5 NiFeOx and Na0.1HemTa1.0NiFeOx respectively. Charge carrier dynamics analysis studied by intensity modulated photocurrent spectroscopy revealed that the PEC enhancement in both systems is mainly associated with improved charge separation efficiency.

Enhanced Power Generation Using a Dual-Surface-Modified Hematite Photoanode in a Direct Glyphosate Photo Fuel Cell.

Given the current and escalating global energy and environmental concerns, this work explores an innovative approach to mitigate a widely employed commercial herbicide using a direct glyphosate (Gly) photocatalytic fuel cell (PFC). The device generates power continuously by converting solar radiation, degrading and mineralizing commercial glyphosate-based fuel, and reducing sodium persulfate at the cathode. Pristine and modified hematite photoanodes were coupled to Pt/C nanoparticles dispersed in a carbon paper (CP) support (Pt/C/CP) dark cathode by using an H-type cell. The Gly/persulfate PFC shows a remarkable current and power generation enhancement after dual-surface modification of pristine hematite with segregated Hf and FeNiOx cocatalysts. The optimized photoanode elevates maximum current density (Jmax) from 0.35 to 0.71 mA cm-2 and maximum power generation (Pmax) from 0.04 to 0.065 mW cm-2, representing 102.85 and 62.50% increase in Jmax and Pmax, respectively, as compared to pristine hematite. The system demonstrated stability over a studied period of 4 h; remarkably, the photodegradation of Gly proved substantial, achieving ∼98% degradation and ∼6% mineralization. Our findings may significantly contribute to reducing Gly's environmental impact in agribusiness since it may convert the pollutant into energy at zero bias. The proposed device offers a sustainable solution to counteract Gly pollution while concurrently harnessing solar energy for power generation.

Collaborative role of co-doping and surface modifying for adjusting surface state of hematite to release the photoelectrochemical activity

Inhibition of bulk and interfacial charge carrier recombination is an urgent solution to release furthest the photoelectrochemical potential abilities of hematite photoelectrode. Herein, the Zr-Y dual metal co-doping engineering and Co/Fe dual metal-organic frameworks cocatalyst layer were employed for modifying hematite photoanode. The novel CoFe-MOF/Zr-Y:Fe2O3 nanoarray composite photoanode exhibits higher PEC activity, the photocurrent density at 1.23 V vs.RHE is increased by 4.7 times than that of the pristine α-Fe2O3. The gain in bulk charge separation efficiency was mainly attributed to the synergistic effect between the two doping ions to improve the electrical conductivity. Wherein, Zr4+ doping endows more free electrons in the bulk α-Fe2O3 and Y3+ introduction causes polaron mobility enhancement. For another, co-doping could reduce the recombination surface state, but form the intermediate surface state to promote hole transfer, thus effectively inhibiting the severe recombination of photogenerated electrons and holes. Furthermore, the CoFe-MOF cocatalyst coating with abundant active sites not only expedites the oxygen evolution reaction kinetics process, but also passivates the surface hole trapping state more thoroughly, resulting in efficient interfacial hole transfer and utilization. This work affords a new collaborative role of co-doping and surface modifying effective avenue for adjusting surface state of hematite to release the photoelectrochemical activity.

Deposition of FeOOH Layer on Ultrathin Hematite Nanoflakes to Promote Photoelectrochemical Water Splitting.

Hematite is one of the most promising photoanode materials for the study of photoelectrochemical (PEC) water splitting because of its ideal bandgap with sufficient visible light absorption and stability in alkaline electrolytes. However, owing to the intrinsically high electron-hole recombination, the PEC performance of hematite is still far below that expected. The efficient charge separation can be achieved via growth of FeOOH on hematite photoanode. In this study, hematite nanostructures were successfully grown on the surface of iron foil by the simple immersion deposition method and thermal oxidation treatment. Furthermore, cocatalyst FeOOH was successfully added to the hematite nanostructure surface to improve charge separation and charge transfer, and thus promote the photoelectrochemical water splitting. By utilizing the FeOOH overlayer as a cocatalyst, the photocurrent density of hematite exhibited a substantial 86% increase under 1.5 VRHE, while the onset potential showed an apparent shift towards the cathodic direction. This can be ascribed to the high reaction area for the nanostructured morphology and high electrocatalytic activity of FeOOH that enhanced the amount of photogenerated holes and accelerated the kinetics of water splitting.