Ru-P pair sites boost charge transport in hematite photoanodes for exceeding 1% efficient solar water splitting

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(27)

Опубликована: Июнь 26, 2023

Fast transport of charge carriers in semiconductor photoelectrodes are a major determinant the solar-to-hydrogen efficiency for photoelectrochemical (PEC) water slitting. While doping metal ions as single atoms/clusters has been popularly used to regulate their transport, PEC performances often low due limited mobility and severe recombination. Here, we disperse Ru P diatomic sites onto hematite (DASs Ru-P:Fe 2 O 3 ) construct an efficient photoelectrode inspired by concept correlated single-atom engineering. The resultant photoanode shows superior photocurrent densities 4.55 6.5 mA cm −2 at 1.23 1.50 V RHE , low-onset potential 0.58 high applied bias photon-to-current conversion 1.00% under one sun illumination, which much better than pristine Fe . A detailed dynamic analysis reveals that remarkable synergetic ineraction reduced recombination concentration with substitution site well construction Ru-P bonds material increases carrier separation fast transportation dynamics. systematic simulation study further proves superiority compared Ru-O bonds, allows more long-lived participate oxidation reaction. This work offers effective strategy enhancing dynamics constructing pair into semiconductors, may be extended other solar splitting.

Язык: Английский

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Tungstate Intercalated NiFe Layered Double Hydroxide Enables Long‐Term Alkaline Seawater Oxidation

Small, Год журнала: 2024, Номер 20(28)

Опубликована: Фев. 16, 2024

Abstract Renewable electricity‐driven seawater splitting presents a green, effective, and promising strategy for building hydrogen (H 2 )‐based energy systems (e.g., storing wind power as H ), especially in many coastal cities. The abundance of Cl − seawater, however, will cause severe corrosion anode catalyst during the electrolysis, thus affect long‐term stability catalyst. Herein, oxidation performances NiFe layered double hydroxides (LDH), classic oxygen (O ) evolution material, can be boosted by employing tungstate (WO 4 2– intercalated guest. Notably, insertion WO 2− to LDH layers upgrades reaction kinetics selectivity, attaining higher current densities with ≈100% O generation efficiency alkaline seawater. Moreover, after 350 h test at 1000 mA cm −2 , only trace active chlorine detected electrolyte. Additionally, follows lattice mechanism on .

Язык: Английский

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Single‐Atomic‐Site Platinum Steers Middle Hydroxyl Selective Oxidation on Amorphous/Crystalline Homojunction for Photoelectrochemical Glycerol Oxidation Coupled with Hydrogen Generation

Advanced Functional Materials, Год журнала: 2024, Номер 34(26)

Опубликована: Фев. 28, 2024

Abstract Photoelectrochemical (PEC) organic conversion is a promising approach to convert low‐cost organics value‐added chemicals, which urgently needs the development of efficient and highly selective photoanodes. Here, Pt single‐atom dispersed WO 3 amorphous/crystalline homojunction for anodic glycerol oxidation reaction (GOR) coupled with cathodic hydrogen generation reported. In photoelectrocatalytic system, novel Pt‐SA/WO x photoanode reaches photocurrent density 2.85 mA cm −2 at 1.2 V versus RHE, up 297.3 mmol m h −1 rate 60.2% dihydroxyacetone (DHA) selectivity, realizing green synthesis high‐value chemicals. The experimental data theoretical calculations reveal regulated band structure, build‐in electric field, surface charge , can improve carrier lifetime, accelerate transfer, reduce energy barrier GOR process, thus boosting PEC activity DHA selectivity. This work provides feasible plan designing atomic‐level engineering constructing on photoanodes products from biomass.

Язык: Английский

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Stacked High‐Entropy Hydroxides Promote Charge Transfer Kinetics for Photoelectrochemical Water Splitting

Advanced Functional Materials, Год журнала: 2024, Номер 34(40)

Опубликована: Май 2, 2024

Abstract Although various kinds of cocatalyst are developed and decorated on the bismuth vanadate (BiVO 4 ) photoanode, its photoelectrochemical (PEC) water splitting performance is limited owing to severe charge recombination sluggish oxygen evolution reaction (OER). Herein, a high‐entropy hydroxide electrocatalyst (FeCoNiMoCrOOH) constructed as co‐catalyst deposited BiVO with good PEC activity stability in potassium borate buffer, addressing substantial poor surface material. FeCoNiMoCrOOH synthesized by simple electrodeposition stacking strategy, delivers an overpotential 172 mV at 10 mA cm −2 600 h under alkaline conditions, representing one best performances high‐entropy‐based catalysts. The FeCoNiMoCrOOH/BiVO photoanode shows photocurrent density 5.23 1.23 V RHE 100 durability buffer. Experimental investigations theoretical calculations demonstrate that synergistic effect Mo Cr FeCoNi catalyst effectively decreases dissolution Fe, Co, Ni after long‐term operation, increases transfer kinetics, promotes OER performances, therefore enhancing photocorrosion resistance . This work provides new avenue design high entropy‐based electrocatalysts boosting solar stability.

Язык: Английский

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Solar-driven highly selective conversion of glycerol to dihydroxyacetone using surface atom engineered BiVO4 photoanodes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 28, 2024

Abstract Dihydroxyacetone is the most desired product in glycerol oxidation reaction because of its highest added value and large market demand among all possible products. However, selectively oxidative secondary hydroxyl groups for highly efficient dihydroxyacetone production still poses a challenge. In this study, we engineer surface BiVO 4 by introducing bismuth-rich domains oxygen vacancies (Bi-rich 4-x ) to systematically modulate adsorption enhance photo-induced charge separation photoelectrochemical into conversion. As result, Bi-rich increases photocurrent density from 1.42 4.26 mA cm −2 at 1.23 V vs. reversible hydrogen electrode under AM 1.5 G illumination, as well selectivity 54.0% 80.3%, finally achieving rate 361.9 mmol m h −1 that outperforms reported values. The atom customization opens way regulate solar-driven organic transformation pathway toward carbon chain-balanced product.

Язык: Английский

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BiVO4 photoanodes with enhanced photoelectrochemical performance: Preparation, modification and emerging applications

Journal of Material Science and Technology, Год журнала: 2024, Номер 217, С. 182 - 220

Опубликована: Сен. 3, 2024

Язык: Английский

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Enhanced Charge Carrier Dynamics on Sb₂Se₃ Photocathodes for Efficient Photoelectrochemical Nitrate Reduction to Ammonia

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(11)

Опубликована: Янв. 16, 2024

Abstract Ammonia (NH 3 ) is recognized as a transportable carrier for renewable energy fuels. Photoelectrochemical nitrate reduction reaction (PEC NO RR) offers sustainable solution nitrate‐rich wastewater treatment by directly converting solar to ammonia. In this study, we demonstrate the highly selective PEC ammonia production from RR constructing CoCu/TiO 2 /Sb Se photocathode. The constructed photocathode achieves an Faraday efficiency (FE) of 88.01 % at −0.2 V RHE and yield high 15.91 μmol h −1 cm −2 −0.3 with excellent onset potential 0.43 . Dynamics experiments theoretical calculations have demonstrated that possesses light absorption capacity, transfer capability, charge separation efficiencies. can effectively adsorb reactant − intermediate, CoCu co‐catalyst increases maximum Gibbs free difference between HER. Meanwhile, Co species enhances spin density Cu, states near Fermi level in pdos, which results activity on This work provides new avenue feasibility efficient synthesis wastewater.

Язык: Английский

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Constructing Sequential Type II Heterojunction CQDs/Bi₂S₃/TiNbO Photoanode with Superior Charge Transfer Capability Toward Stable Photoelectrochemical Water Splitting

ACS Applied Materials & Interfaces, Год журнала: 2024, Номер 16(13), С. 16062 - 16074

Опубликована: Март 25, 2024

Efficient charge transfer and light-trapping units are pivotal prerequisites in the realm of Ti-based photoanode photoelectrochemical (PEC) water splitting. In this work, we successfully synthesized a ternary carbon quantum dots/Bi2S3 dots/Nb-doped TiO2 nanotube arrays (CQDs/Bi2S3/TiNbO) composite for PEC CQDs/Bi2S3/TiNbO exhibited considerably elevated photocurrent density 8.80 mA cm–2 at 1.23 V vs reversible hydrogen electrode, which was 20.00 times better than that (0.44 cm–2). Furthermore, attested to exceptional stability, maintaining 92.54% its initial current after 5 h stability measurement. Nb-doping boosted electrical conductivity, facilitating solid–liquid interface. Moderate amounts Bi2S3 dots (QDs) CQDs deposited on TiNbO provided abundant active sites electrolyte–photoanode interaction. Simultaneously, QDs synergistically functioned as broaden light absorption range from 396 530 nm, stimulating increased carrier generation within photoanode. comparison with pristine TiO, photoanodes possessed superior ability promote interfacial reactions. This study may provide strategy developing high-performance efficient trapping highly driving solar-to-hydrogen conversion.

Язык: Английский

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Efficient Photoelectrocatalysis of Glycerol to Dihydroxyacetone and Synergistic Hydrogen Generation via Dual Oxidation Pathways Using Co-LDH/Bi₂O₃/TiO₂ Ternary Array

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 2124 - 2138

Опубликована: Янв. 22, 2025

Replacing the oxygen evolution reaction (OER) in photoelectrocatalytic (PEC) water splitting with glycerol oxidation (GOR) not only enhances hydrogen production but also generates high-value byproducts. In this study, we developed a ternary photoanode, Co-LDH/Bi2O3/TiO2, by loading particulate Bi2O3 and linear Co-LDH onto TiO2 nanorod for conversion production. The characterization results confirm formation of coupled interfaces between TiO2, which improves visible light utilization promotes type II heterojunctions, resulting significant suppression electron–hole recombination an improvement PEC performance. Fourier transform infrared (FT-IR) spectroscopy revealed that Co-LDH/Bi2O3/TiO2 photoanode exhibited stronger adsorption intermediate hydroxyl group more effective desorption DHA compared to binary photoanodes (Co-LDH/TiO2 Bi2O3/TiO2), high-selectivity DHA. Mechanistic studies density function theory calculations have shown Co-LDH/TiO2 oxidizes mainly through hole oxidation, Bi2O3/TiO2 radical (•OH) oxidation. Therefore, constructed (Co-LDH/Bi2O3/TiO2) dual heterojunction converts pathways •OH This work demonstrates promising strategy developing high-performance systems production, leveraging synergistic effects multisemiconductor heterojunctions multiple pathways, offering potential practical applications.

Язык: Английский

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Metal‐Organic Framework Glass Catalysts from Melting Glass‐Forming Cobalt‐Based Zeolitic Imidazolate Framework for Boosting Photoelectrochemical Water Oxidation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(32)

Опубликована: Июнь 2, 2023

Abstract Sluggish oxygen evolution kinetics and serious charge recombination restrict the development of photoelectrochemical (PEC) water splitting. The advancement novel metal–organic frameworks (MOFs) catalysts bears practical significance for improving PEC splitting performance. Herein, a MOF glass catalyst through melting glass‐forming cobalt‐based zeolitic imidazolate framework (Co‐a g ZIF‐62) was introduced on various metal oxide (MO: Fe 2 O 3 , WO BiVO 4 ) semiconductor substrates coupled with NiO hole transport layer, constructing integrated Co‐a ZIF‐62/NiO/MO photoanodes. Owing to excellent conductivity, stability open active sites glass, photoanodes exhibit significantly enhanced oxidation activity in comparison pristine MO From experimental analyses density functional theory calculations, ZIF‐62 can effectively promote transfer separation, improve carrier mobility, accelerate reaction (OER), thus This not only serves as an OER cocatalyst tunable photoelectrodes, but also enables promising opportunities devices solar energy conversion.

Язык: Английский

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