Ultrastable halide perovskite CsPbBr3 photoanodes achieved with electrocatalytic glassy-carbon and boron-doped diamond sheets
At a Glance
Section titled âAt a Glanceâ| Metadata | Details |
|---|---|
| Publication Date | 2024-03-30 |
| Journal | Nature Communications |
| Authors | Zhonghui Zhu, MĂĄtyĂĄs DabĂłczi, M. J. Chen, Yimin Xuan, Xianglei Liu |
| Institutions | Imperial College London, Nanjing University of Aeronautics and Astronautics |
| Citations | 22 |
| Analysis | Full AI Review Included |
Executive Summary
Section titled âExecutive SummaryâThis research presents a breakthrough in stabilizing halide perovskite photoanodes (CsPbBr3) for solar-driven Oxygen Evolution Reaction (OER) in aqueous electrolytes, achieving record operational lifetimes.
- Record Stability: The photoanodes achieved unprecedented operational stability, preserving 97% of the initial photocurrent density (7.4 mA/cm2) for 210 hours (BDD sheets) and 95% for 168 hours (GC sheets) of continuous operation at 1.23 VRHE.
- Multifunctional Protection: Stability is achieved using highly conductive, impermeable protective sheetsâBoron-Doped Diamond (BDD) or Glassy Carbon (GC)âwhich are intrinsically stable against corrosion and mechanical stress.
- Electrocatalytic Enhancement: The protective sheets are functionalized with electrodeposited Ni nanopyramids (to increase surface area and charge injection) and a highly active NiFeOOH OER catalyst.
- High Performance: The devices exhibit low solar-driven OER onset potentials (as low as +0.45 VRHE) and high photocurrent densities (up to 7.4 mA/cm2), owing to the excellent conductivity of BDD/GC and the catalytic activity of NiFeOOH.
- Modular and Scalable Design: The photo-absorber (FTO/SnO2/CsPbBr3/Carbon) and the protective catalytic sheet (Adhesive/GC or BDD/Ni/NiFeOOH) are fabricated separately and joined using a simple spin-coated adhesive, ensuring electrical contact and allowing for reusability of the protective sheets.
- Earth-Abundant Materials: The protective and catalytic components rely solely on earth-abundant elements (carbon, nickel, iron, oxygen), supporting commercial viability.
Technical Specifications
Section titled âTechnical Specificationsâ| Parameter | Value | Unit | Context |
|---|---|---|---|
| Operational Stability (BDD) | 210 | h | Continuous OER at 1.23 VRHE |
| Photocurrent Retention (BDD) | 97 | % | After 210 h stability test |
| Photocurrent Density (BDD) | 7.4 | mA/cm2 | Initial stabilized value at 1.23 VRHE |
| Operational Stability (GC) | 168 | h | Continuous OER at 1.23 VRHE |
| Photocurrent Retention (GC) | 95 | % | After 168 h stability test |
| OER Onset Potential (GC) | +0.45 | VRHE | Solar-driven OER |
| OER Onset Potential (BDD) | +0.46 | VRHE | Solar-driven OER |
| Maximum ABPE (BDD) | 3.84 | % | Applied Bias Photon-to-Current Efficiency at +0.6 VRHE |
| Faradaic Efficiency (OER) | ~91 | % | Average O2 production efficiency |
| CsPbBr3 Bandgap | 2.3 | eV | Measured by IPCE onset |
| GC Resistivity | 45 | ”Ω m | Protective sheet material |
| BDD Resistivity | 10 | ”Ω m | Protective sheet material |
| Ni Nanopyramid Base Size | 300-500 | nm | Average dimension |
| NiFeOOH Deposition Charge | 4.2 | mC/cm2 | Electrodeposition parameter |
| Electrolyte | 1 | M | NaOH (pH 14) |
Key Methodologies
Section titled âKey MethodologiesâThe photoanode is constructed modularly, separating the photo-absorber device (FTO/SnO2/CsPbBr3/Carbon) from the protective catalytic sheet (Adhesive/GC or BDD/Ni/NiFeOOH).
- SnO2 Electron Transport Layer (ETL): Deposited on FTO glass via Chemical Bath Deposition (CBD) at 90 °C for 4 hours, using tin chloride dihydrate and urea precursors.
- CsPbBr3 Absorber Layer: Fabricated using a two-step solution deposition: PbBr2 spin coating (2000 rpm) followed by immersion in a CsBr methanol solution (5 min at 50 °C), and subsequent annealing at 250 °C.
- Carbon Electrode: Mesoporous carbon paste was blade-coated onto the CsPbBr3 layer and annealed at 70 °C.
- GC Sheet Roughening: The front side of commercial GC sheets was mechanically roughened using silicon carbide (600 Grit) and fine alumina slurries (0.3 ”m, then 0.05 ”m) to enhance surface area and adhesion. (BDD sheets were used with their rough side as-received).
- Ni Nanopyramid Electrodeposition: Ni was electrodeposited onto the roughened GC/BDD surface at 60 °C by applying 10 mA/cm2 for 10 minutes in a nickel sulfamate bath (two-electrode setup).
- NiFeOOH Catalyst Electrodeposition: NiFeOOH was deposited via linear sweep voltammetry (LSV) from +0.6 V to +1.2 V (20 mV/s) until a charge density of 4.2 mC/cm2 was achieved, using nickel and iron sulfate precursors (three-electrode setup).
- Device Integration: A thin adhesive layer (commercial adhesive diluted 1:3 in toluene) was spin-coated onto the back (flat) side of the protective sheet and manually pressed onto the printed carbon layer of the photo-absorber device to ensure electrical contact.
Commercial Applications
Section titled âCommercial ApplicationsâThe development of ultrastable, high-performance photoanodes using robust carbon and diamond materials opens doors for commercial applications in sustainable energy and chemical production.
- Solar Fuels Production: Direct conversion of solar energy into chemical fuels, primarily hydrogen (H2) via water splitting, meeting the commercialization target efficiency of >10% (when coupled with a stable cathode).
- Photoelectrochemical (PEC) Cells: Implementation in durable PEC reactors for large-scale production of oxygen and other valuable chemicals from water or CO2 conversion.
- High-Stability Electrodes: Use of BDD and GC sheets as robust, corrosion-resistant electrode substrates in harsh chemical environments (e.g., high pH electrolytes).
- Industrial Wastewater Treatment: BDD electrodes are highly effective for electrochemical oxidation (EO) of recalcitrant organic pollutants, leveraging their wide potential window and chemical inertness.
- Catalyst Support Systems: The Ni nanopyramid structure provides a high surface area, stable platform for OER catalysts (NiFeOOH), applicable in industrial electrolyzers.
- Durable Sensor Technology: Utilizing the chemical and mechanical stability of BDD/GC in corrosive media for long-term monitoring and sensing applications.
View Original Abstract
Abstract Halide perovskites exhibit exceptional optoelectronic properties for photoelectrochemical production of solar fuels and chemicals but their instability in aqueous electrolytes hampers their application. Here we present ultrastable perovskite CsPbBr 3 -based photoanodes achieved with both multifunctional glassy carbon and boron-doped diamond sheets coated with Ni nanopyramids and NiFeOOH. These perovskite photoanodes achieve record operational stability in aqueous electrolytes, preserving 95% of their initial photocurrent density for 168 h of continuous operation with the glassy carbon sheets and 97% for 210 h with the boron-doped diamond sheets, due to the excellent mechanical and chemical stability of glassy carbon, boron-doped diamond, and nickel metal. Moreover, these photoanodes reach a low water-oxidation onset potential close to +0.4 V RHE and photocurrent densities close to 8 mA cm â2 at 1.23 V RHE , owing to the high conductivity of glassy carbon and boron-doped diamond and the catalytic activity of NiFeOOH. The applied catalytic, protective sheets employ only earth-abundant elements and straightforward fabrication methods, engineering a solution for the success of halide perovskites in stable photoelectrochemical cells.