Exciton Binding Energy Research Articles

Exploring structure-property landscape of non-fullerene acceptors for organic solar cells.

We present a comprehensive analysis of the structure-property relationship in small molecule non-fullerene acceptors (NFAs) featuring an acceptor-donor-acceptor configuration employing state-of-the-art quantum chemical computational methods. Our focus lies in the strategic functionalization of halogen groups at the terminal positions of NFAs as an effective means to mitigate non-radiative voltage losses and augment photovoltaic and photophysical properties relevant to organic solar cells. Through photophysical studies, we observe a bathochromic shift in the visible region for all halogen-functionalized NFAs, except type-2, compared to the unmodified compound. Most of these functionalized compounds exhibit exciton binding energies below 0.3eV and ΔLUMO less than 0.3eV, indicating their potential as promising candidates for organic solar cells. Selected candidate structures undergo an analysis of charge transport properties using the semi-classical Marcus theory based on hopping transport formalism. Molecular dynamics simulations followed by charge transport simulations reveal an ambipolar nature of charge transport in the investigated NFAs, with equivalent hole and electron mobilities compared to the parent compound. Our findings underscore the crucial role of end-group functionalization in enhancing the photovoltaic and photophysical characteristics of NFAs, ultimately improving the overall performance of organic solar cells. This study advances our understanding of the structure-property relationships in NFAs and provides valuable insights into the design and optimization of organic solar cell materials.

Defect Engineering Simultaneously Regulating Exciton Dissociation in Carbon Nitride and Local Electron Density in Pt Single Atoms Toward Highly Efficient Photocatalytic Hydrogen Production.

The high exciton binding energy (Eb) and sluggish surface reaction kinetics have severely limited the photocatalytic hydrogen production activity of carbon nitride (CN). Herein, a hybrid system consisting of nitrogen defects and Pt single atoms is constructed through a facile self-assembly and photodeposition strategy. Due to the acceleration of exciton dissociation and regulation of local electron density of Pt single atoms along with the introduction of nitrogen defects, the optimized Pt-MCT-3 exhibits a hydrogen production rate of 172.0µmolh-1 (λ ≥ 420nm), ≈41 times higher than pristine CN. The apparent quantum yield for the hydrogen production is determined to be 27.1% at 420nm. The experimental characterizations and theoretical calculations demonstrate that the nitrogen defects act as the electron traps for the exciton dissociation, resulting in a decrease of Eb from 86.92 to 43.20meV. Simultaneously, the stronger interaction between neighboring nitrogen defects and Pt single atoms directionally drives free electrons to aggregate around Pt single atoms, and tailors the d-band electrons of Pt, forming a moderate binding strength between Pt atoms and H* intermediates.

Efficient Charge Transport in Inverted Perovskite Solar Cells via 2D/3D Ferroelectric Heterojunction.

While the 2D/3D heterojunction is an effective method to improve the power conversion efficiency (PCE) of perovskite solar cells (PSCs), carriers are often confined in the quantum wells (QWs) due to the unique structure of 2D perovskite, which makes the charge transport along the out-of-plane direction difficult. Here, a 2D/3D ferroelectric heterojunction formed by 4,4-difluoropiperidine hydrochloride (2FPD) in inverted PSCs is reported. The enriched 2D perovskite (2FPD)2PbI4 layer with n = 1 on the perovskite surface exhibits ferroelectric response and has oriented dipoles along the out-of-plane direction. The ferroelectricity of the oriented dipole layer facilitates the enhancement of the built-in electric field (1.06 V) and the delay of the cooling process of hot carriers, reflected in the high carrier temperature (above 1400 K) and the prolonged photobleach recovery time (139.85 fs, measured at bandgap), improving the out-of-plane conductivity. In addition, the alignment of energy levels is optimized and exciton binding energy (32.8 meV) is reduced by changing the dielectric environment of the surface. Finally, the 2FPD-treated PSCs achieve a PCE of 24.82% (certified: 24.38%) with the synergistic effect of ferroelectricity and defect passivation, while maintaining over 90% of their initial efficiency after 1000 h of maximum power point tracking.

Promoting exciton dissociation by metal ion modification in polymeric carbon nitride for photocatalysis

Carbon nitride, a typical low-dimensional conjugated polymer photocatalyst, features a high exciton binding energy due to the weak dielectric screening and the strong Coulombic attraction of photogenerated electrons and holes. The reduction of the exciton binding energy of carbon nitride to promote the conversion from excitons into free carriers is the first priority for the improvement of charge-transfer-dependent photocatalytic reaction activity. In this paper, by introducing a variety of polar metal cations to carbon nitride, it is demonstrated that the charge distribution of the heptazine ring can be improved by ion polarization, which effectively promotes the dissociation of excitons into electrons and holes. The sodium ion shows the best modification effect, which enhances the rate of both photocatalytic hydrogen and hydrogen peroxide production by about 50%. Characterization shows that the introduction of strongly polar metal cations contributes to the reduction of the exciton dissociation energy of carbon nitride. This study provides a new perspective and a convenient method for the exciton modulation engineering of low-dimensional photocatalysts.

Effect of metal (Cr, Sr, Ag, Cu) doping on the performance of lead-free RbSnI3 based perovskite solar cells: A theoretical approach

Perovskite solar cells based on lead have witnessed unprecedented growth over the past decade, achieving an impressive power conversion efficiency (PCE) of 26.1%. However, lead toxicity remains a concern for commercialization. In order to resolve the matter, scientists have been investigating alternative materials; in this context, rubidium-based lead-free perovskites like RbSnI3 may be a promising alternative because it has a high optical conductivity and absorption coefficient. Density Functional Theory (DFT)-based first-principles studies are used in this work to examine the effect of metal doping (specifically Cr, Sr, Ag, and Cu) on the optoelectronic and structural characteristics of orthorhombic RbSnI3 perovskite. In addition, we conducted a comprehensive study to investigate the impact of metal doping on the formation energy, structural stability, and HOMO–LUMO energy levels of RbSnI3 perovskite. Introducing transition metal cations (Cr2+, Ag+, and Cu+) at the Rb site results in a flat band in the conduction band region, transforming the RbSnI3’s indirect band gap into a direct one and significantly affecting the optoelectronic properties. The DFT results are then integrated into the Solar Cell Capacitance Simulator (SCAPS-1D) to estimate the effectiveness of the modeled device. The Cu-doped RbSnI3 device exhibits the highest PCE of 20.2%. Furthermore, Ag and Cu doping in RbSnI3 increases bond length, which reduces exciton binding energy and helps with charge carrier generation.

Direct Observation of Circularly Polarized Nonlinear Optical Activities in Chiral Hybrid Lead Halides.

Circularly polarized light emission is a crucial application in imaging, sensing, and photonics. However, utilizing low-energy photons to excite materials, as opposed to high-energy light excitation, can facilitate deep-tissue imaging and sensing applications. The challenge lies in finding materials capable of directly generating circularly polarized nonlinear optical effects. In this study, we introduce a chiral hybrid lead halide (CHLH) material system, R/S-DPEDPb3Br8·H2O (DPED = 1,2-diphenylethylenediammonium), which can directly produce circularly polarized second harmonic generation (CP-SHG) through linearly polarized infrared light excitation, exhibiting a polarization efficiency as high as 37% at room temperature. To understand the spin relaxation mechanisms behind the high polarization efficiency, we utilized two models, so-called D'yakonov-Perel' (DP) and Bir-Aronov-Pikus (BAP) mechanisms. The unique zigzag inorganic frameworks within the hybrid structure are believed to reduce the dielectric confinement and exciton binding energy, thus enhancing spin polarization, especially in regions with a high excitation pump fluence based on the DP mechanism. In the case of low excitation pump fluence, the BAP mechanism dominates, as evidenced by the observed decrease in the polarization ratio from CP-SHG measurement. Using density functional theory analysis, we elucidate how the distinctive 8-coordination environment of lead bromide building blocks effectively suppresses spin-orbit coupling at the conduction band minimum. This suppression significantly diminishes spin-splitting, thereby slowing the spin relaxation rate.

Exploring layer thinning of exfoliated β-tellurene and room temperature photoluminescence with large exciton binding energy revealed in β-TeO2

Due to its tunable bandgap, anisotropic behavior, and superior thermoelectric properties, device applications using layered tellurene (Te) are becoming more attractive. Here, we report a thinning technique for exfoliated tellurene nanosheets using thermal annealing in an oxygen environment. We characterize different thinning parameters, including temperature and annealing time. Based on our measurements, we show that controlled layer thinning occurs in the narrow temperature range of 325–350 °C. We also show a reliable method to form β-tellurene oxide (β-TeO2), which is an emerging wide bandgap semiconductor with promising electronic and optoelectronic properties. This wide bandgap semiconductor exhibits a broad photoluminescence (PL) spectrum with multiple peaks covering the range of 1.76–2.08 eV. This PL emission, coupled with Raman spectra, is strong evidence of the formation of 2D β-TeO2. We discuss the results obtained and the mechanisms of Te thinning and β-TeO2 formation at different temperature regimes. We also discuss the optical bandgap of β-TeO2 and show the existence of pronounced excitonic effects evident by the large exciton binding energy in this 2D β-TeO2 system that reach 1.54–1.62 eV for bulk and monolayer, respectively. Our work can be utilized to have better control over the Te nanosheet thickness. It also sheds light on the formation of well-controlled β-TeO2 layered semiconductors for electronic and optoelectronic applications.

Photocatalytic benzylamine coupling dominated by modulation of linkers in donor-acceptor covalent organic frameworks

The strong excitonic effect is widely prevalent in covalent organic frameworks (COFs)-based catalysts, while the high exciton binding energies (Eb) of COFs seriously limit their photocatalytic performance. Herein, theoretical calculations are conducted to evaluate the Eb values of potential COFs derived from benzo[1,2-b:3,4-b'-b'']trithiophene-2,5,8-tricarbaldehyde (BTT) and 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde (Bp) as aldehyde monomers. Diverse aromatic amine linkers including dipyridine diamine (BPy), biphenyl diamine (BPh), and p-phenylenediamine (MPh) with different molecular lengths and N-sites are used as linker models to regulate the excitonic effect. The obtained BTT-BPy-COF with a long BPy linker and the lowest calculated Eb value possesses the best photocatalytic performance for benzylamine coupling, with conversion and selectivity up to 99% accompanied by a high oxidation rate, outperforming most of the reported works. Further mechanistic investigation reveals that the bipyridine-N sites in BTT-BPy-COF exhibit strong electron transfer as well as enhanced O2 adsorption and activation that is beneficial to photocatalytic benzylamine coupling.

Highly efficient deep-blue emitting CsPbBr3 nanoplatelets synthesized via surface ligand-mediated strategy

Two-dimensional (2D) CsPbBr3 nanoplatelets (NPLs) have attracted great attention as one of promising semiconductor nanomaterials due to their large exciton binding energy and narrow emission spectra. However, the labile ionic and weakly bound surfaces of deep-blue emitting CsPbBr3 NPLs with wide bandgap result in their colloidal instability, thus degrading their optical properties. It is challenging to obtain deep-blue emitting CsPbBr3 NPLs with excellent optical properties. In this study, high-quality blue-emitting CsPbBr3 NPLs with tunable thickness were prepared adopting the DBSA-mediated confinement effect based on the hot-injection method. Thanks to the coordination interaction of − SO3− of DBSA ligand and the Pb2+ on the surface of the CsPbBr3 NPLs, as well as the effective passivation of Br vacancy defects on the surface of NPLs by OAm-Br, the obtained pure-blue CsPbBr3 NPLs and deep-blue CsPbBr3 NPLs show high photoluminescence quantum yield (PLQY) of 92 % and 81.2 %, respectively. To the best of our knowledge, this is the highest PLQY recorded for deep-blue emitting CsPbBr3 NPLs with two monolayers [PbBr6]4− octahedra. Furthermore, the agglomeration of CsPbBr3 NPLs due to ligand loss induced by moisture, oxygen, and irradiation was also suppressed by the dual passivation effect of DBSA and OAm-Br. Our work provided a new approach to developing high-performance and stable deep-blue emitting CsPbBr3 perovskite nanoplatelets.

Carrier Transport in Low‐Dimensional Tin Perovskite Solar Cells

Recently, the emerging of low‐dimensional tin perovskite solar cells (TPSCs) by introducing bulky organic spacers has attracted extensive attention. It can not only inhibit the oxidation of Sn2+, but also reduce the ion migration and self‐doping effect. Thanks to these advantages, the TPSCs have achieved an impressive power conversion efficiency (PCE) of over 15% recently. However, the introduction of organic spacers impedes the carrier transport and thus limits the attainable PCE. Therefore, it is important to understand the carrier‐transport mechanism in low‐dimensional perovskite to develop more efficient and stable TPSCs. In this review, the latest progress of carrier transport in low‐dimensional TPSCs is summarized in detail. First, the characteristics of carrier transport in low‐dimensional tin perovskites are discussed. Then, the strategies to improve carrier transport are discussed, mainly from the aspects of crystal orientation, crystallization kinetics, defects, interface energy level alignment, quantum well effect, and exciton binding energy. Finally, the future challenges and prospects are expounded to prepare high‐performance and stable low‐dimensional TPSCs.

Enhanced charge transport in 2D inorganic molecular crystals constructed with charge‐delocalized molecules

AbstractOutstanding charge transport in molecular crystals is of great importance in modern electronics and optoelectronics. The widely adopted strategies to enhance charge transport, such as restraining intermolecular vibration, are mostly limited to organic molecules, which are nearly inoperative in 2D inorganic molecular crystals currently. In this contribution, charge transport in 2D inorganic molecular crystals is improved by integrating charge‐delocalized Se8 rings as building blocks, where the delocalized electrons on Se8 rings lift the intermolecular orbitals overlap, offering efficient charge transfer channels. Besides, α‐Se flakes composed of charge‐delocalized Se8 rings possess small exciton binding energy. Benefitting from these, α‐Se flake exhibits excellent photodetection performance with an ultrafast response rate (~5 μs) and a high detectivity of 1.08 × 1011 Jones. These findings contribute to a deeper understanding of the charge transport of 2D inorganic molecular crystals composed of electron‐delocalized inorganic molecules and pave the way for their potential application in optoelectronics.

Positional isomerism engineering toward minimizing exciton binding energy in sulfone copolymers for enhanced uranyl photoreduction

Conjugated microporous polymers (CMPs) have emerged as promising platforms for photocatalytic separation and enrichment of radionuclides. However, the development of CMPs with efficient exciton dissociation and free charge generation is still highly hindered by their high exciton binding energy (Eb). Herein, for the first time, three sulfone-containing CMPs are fabricated to regulate Eb by position isomerism of altering linkage sites. Temperature-dependent photoluminescence spectra reveals that ECUT-3,7-SO with 3,7-site linkage achieves a diminished Eb of 40.1 meV. DFT calculation complementally demonstrate that the Eb is related to its strongly polarized electric field and large conjugation degree, which can be easily regulated via position isomerism of its building blocks. Among the three, ECUT-3,7-SO exhibits a completely conjugated structure and a large molecular dipole moment, thus significantly reducing the Eb. As a result, ECUT-3,7-SO exhibits the highest photoreduction uranium rate constant (k, T = 298.15 K) of 0.081 min−1, and the maximum uranium extraction capacity of 918.0 mg g−1 under visible-light irradiation. This work highlights the importance of positional isomerization to the development of low exciton binding energy photocatalyst for uranium resource field.

Excitons, optical spectra, and electronic properties of semiconducting Hf-based MXenes.

Semiconducting MXenes are an intriguing two-dimensional (2D) material class with promising electronic and optoelectronic properties. Here, we focused on recently prepared Hf-based MXenes, namely, Hf3C2O2 and Hf2CO2. Using the first-principles calculation and excited state corrections, we proved their dynamical stability, reconciled their semiconducting behavior, and obtained fundamental gaps by using the many-body GW method (indirect 1.1 and 2.2eV; direct 1.4 and 3.5eV). Using the Bethe-Salpeter equation, we subsequently provided optical gaps (0.9 and 2.7eV, respectively), exciton binding energies, absorption spectra, and other properties of excitons in both Hf-based MXenes. The indirect character of both 2D materials further allowed for a significant decrease of excitation energies by considering indirect excitons with exciton momentum along the Γ-M path in the Brillouin zone. The first bright excitons are strongly delocalized in real space while contributed by only a limited number of electron-hole pairs around the M point in the k-space from the valence and conduction band. A diverse range of excitonic states in Hf3C2O2 MXene lead to a 4% and 13% absorptance for the first and second peaks in the infrared region of absorption spectra, respectively. In contrast, a prominent 28% absorptance peak in the visible region appears in Hf2CO2 MXene. Results from radiative lifetime calculations indicate the promising potential of these materials in optoelectric devices requiring sustained and efficient exciton behavior.

Inorganic-Organic Hybrid Layered Semiconductor AgSePh: Quasi-Solution Synthesis, Optical Properties, and Thermolysis Behavior.

Two-dimensional inorganic-organic hybrid layered semiconductors are actively studied because of their naturally formed multiquantum well (MQW) structures and associated optical, photoelectric, and quantum optics characteristics. Silver benzeneselenolate (AgSePh, Ph = C6H5) is a new member of such hybrid layered materials, but has not fully been exploited. Herein, we present a quasi-solution method to prepare high quality free-standing AgSePh flake-like microcrystals by reacting diphenyl diselenide (Ph2Se2) with silver nanoparticles. The resultant AgSePh microflakes exhibit room-temperature (RT) resolvable MQW-induced quasi-particle quantization and interesting optical properties, such as three distinct excitonic resonance absorptions X1 (2.67 eV), X2 (2.71 eV), and X3 (2.83 eV) in the visible region, strong narrow-line width blue photoluminescence at ∼2.64 eV (470 nm) from the radiative recombination of the X1 exciton state, and a large exciton binding energy (∼0.35 eV). Furthermore, AgSePh microcrystals show high stability under water, oxygen, and heat environments, while above 220 °C, they will thermally decompose to silver and Ph2Se2 as evidenced by a combination of thermogravimetry and differential scanning calorimetry and pyrolysis-coupled gas chromatography-mass spectrometry studies. Finally, a comparison is extended between AgSePh and other metal benzeneselenolates, benzenethiolates, and alkanethiolates to clarify differences in their solubility, decomposition/melting temperature, and pyrolytic products.

Quest for the porosity-regulated high dielectric and conductive performance of MOF by introducing nanoparticles: Performance evaluation at elevated temperatures

Metal-organic frameworks (MOFs) are among the novel materials that have drawn a lot of attention from the scientific and technological communities. There have been numerous reports of 3D MOFs in the scientific community, but due to distinct structural and electrical properties, scientists are particularly interested in zinc imidazole framework 8 (ZIF-8). Due to its characteristic low dielectric values, ZIF-8 is an excellent choice for low-dielectric applications. However, the incorporation of nanoparticles can increase the dielectric constant of ZIF-8. In this study, ZnO semiconducting nanoparticles are used as a filler of ZIF-8 due to their exceptionally high electron mobility, exciton binding energy, and wide band gap. We hypothesized that the incorporation of semiconducting nanoparticles (ZnO) inside ZIF-8 influences the porosity, pore size distributions, pore morphology, and interconnectivity of ZIF-8 which influences the polarization of pristine ZIF-8 and helps to increase the dielectric properties. ZnO has inherent ionic polarization which not only enhances the dielectric constant but also simultaneously decreases the dielectric loss which is essential for any dielectric materials. The dielectric constant was enhanced by 1.5 times after 5 wt% ZnO doping in ZIF-8 at room temperature and the enhancement was nearly five times at 150 °C. Simultaneously the dielectric loss decreases after ZnO doping compared to pristine ZIF-8. The tailoring of porosity, the number of pores, the presence of defects and oxygen vacancies are responsible for the modulated dielectric properties. The conductivity of ZIF-8 can also be tuned by the nanoparticles incorporation which indicates the larger production of drift electrons inside MOF in the presence of nanoparticles. The detailed morphological characteristics confirm the interaction between ZnO and ZIF-8. The result is a thorough understanding of the intrinsic and extrinsic electrical properties of ZIF-8 composites for future generations of technology. This work aimed to exploit possibilities of MOF towards high dielectric constant and low loss material by simple nanoparticle incorporation.

A tight-binding model for illustrating exciton confinement in semiconductor nanocrystals.

The Brus equation describes the relation between the lowest energy of an electron-hole pair and the size of a semiconductor crystallite. However, taking the strong confinement regime as a starting point, the equation does not cover the transition from weak to strong confinement, the accompanying phenomenon of charge-carrier delocalization, or the change in the transition dipole moment of the electron-hole pair state. Here, we use a one-dimensional, two-particle Hubbard model for interacting electron-hole pairs that extends the well-known tight-binding approach through a point-like electron-hole interaction. On infinite chains, the resulting exciton states exhibit the known relation between the Bohr radius, the exciton binding energy, and the effective mass of the charge carriers. Moreover, by introducing infinite-well boundary conditions, the model enables the transition of the exciton states from weak to strong confinement to be tracked, while straightforward adaptations provide insights into the relation between defects, exciton localization, and confinement. In addition, by introducing the dipole operator, the variation of the transition dipole moment can be mapped when shifting from electron-hole pairs in strong confinement to delocalized and localized excitons in weak confinement. The proposed model system can be readily implemented and extended to different multi-carrier states, thus providing researchers a tool for exploring, understanding, and teaching confinement effects in semiconductor nanocrystals under different conditions.

2D and 3D Halide Perovskite‐Based Supercapacitors

AbstractMetal halide perovskites (MHPs) are extremely promising materials for energy storage applications. Among them, two‐dimensional (2D) halide perovskites attract much attention for supercapacitor applications because of exciting properties such as electronic confinement, structural flexibility, attractive performance and stability. On the other hand, owing to its low exciton binding energy and long‐range carrier transport nature, three‐dimensional (3D) halide perovskites have been employed as one of the most promising supercapacitor materials. These materials have become one of the highly promising mixed electronic‐ionic material for efficient energy storage devices. 2D and 3D MHPs have distinctive physicochemical and electrochemical characteristics, and capacity to create hetero‐structures to strengthen their electrochemical capabilities. Thus, it is important to understand synthesis, properties and various electrochemical aspects of MHPs and their super‐capacitive behaviors. This review article focuses on the extensive overview of the recent developments of MHPs which have demonstrated exciting possibilities as supercapacitor materials but relatively less explored till now. Our review article comprises of synthesis processes, opto‐electronic properties, mechanism, supercapacitor performances, challenges and opportunities in brief. This review thus thoroughly discusses the importance and intriguing aspect of 2D and 3D halide perovskites as supercapacitor materials for their futuristic energy storage applications.

Ground state structure and optoelectronic properties of novel quasi-2D layered halide perovskites CsPb2X5 (X= Cl, Br, I) via first principle calculations

The ground state structure and optoelectronic properties of novel quasi-2D layered halide perovskites CsPb2X5 (X= Cl, Br, I) are investigated for the possible optoelectronic applications in light emitting, photodetectors, photoemission, and photovoltaic (PV) devices using first principle-based calculations of the density functional theory (DFT). In the structure composition of CsPb2X5, 2Pb2+ atoms coordinated with eight X- anions build [Pb2X5]- polyhedral layers, where two layers of [Pb2X5]- polyhedron are separated by Cs+ (spacer cation) layers. The band gap nature of the studied semiconductors is indirect and spin orbit coupling (SOC) effect reduces the band gaps and splits the Pb-p and X-p orbitals at the edges of conduction and valence bands respectively. The wide and suitable band gaps of CsPb2X5 enable them for advanced technological applications in photodetectors, transistors, and optoelectronic devices. The dielectric functions, exciton binding energies, and carrier's effective masses show that CsPb2X5 are suitable materials for optoelectronic, photodetectors, and light emitting devices.

Mixed‐Linker Strategy for the Construction of Sulfone‐Containing D–A–A Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Peroxide Production

AbstractThe solar‐driven photocatalytic production of hydrogen peroxide (H2O2) from water and oxygen using semiconductor catalysts offers a promising approach for converting solar energy into storable chemical energy. However, the efficiency of photocatalytic H2O2 production is often restricted by the low photo‐generated charge separation, slow surface reactions and inadequate stability. Here, we developed a mixed‐linker strategy to build a donor‐acceptor‐acceptor (D–A–A) type covalent organic framework (COF) photocatalyst, FS‐OHOMe‐COF. The FS‐OHOMe‐COF structure features extended π–π conjugation that improves charge mobility, while the introduction of sulfone units not only as active sites facilitates surface reactions with water but also bolsters stability through increased interlayer forces. The resulting FS‐OHOMe‐COF has a low exciton binding energy, long excited‐state lifetime and high photo‐stability that leads to high performance for photocatalytic H2O2 production (up to 1.0 mM h−1) with an H2O2 output of 19 mM after 72 hours of irradiation. Furthermore, the catalyst demonstrates high stability, which sustained activity over 192 hours of photocatalytic experiment.

Mixed-Linker Strategy for the Construction of Sulfone-Containing D-A-A Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Peroxide Production.

The solar-driven photocatalytic production of hydrogen peroxide (H2O2) from water and oxygen using semiconductor catalysts offers a promising approach for converting solar energy into storable chemical energy. However, the efficiency of photocatalytic H2O2 production is often restricted by the low photo-generated charge separation, slow surface reactions and inadequate stability. Here, we developed a mixed-linker strategy to build a donor-acceptor-acceptor (D-A-A) type covalent organic framework (COF) photocatalyst, FS-OHOMe-COF. The FS-OHOMe-COF structure features extended π-π conjugation that improves charge mobility, while the introduction of sulfone units not only as active sites facilitates surface reactions with water but also bolsters stability through increased interlayer forces. The resulting FS-OHOMe-COF has a low exciton binding energy, long excited-state lifetime and high photo-stability that leads to high performance for photocatalytic H2O2 production (up to 1.0 mM h-1) with an H2O2 output of 19 mM after 72 hours of irradiation. Furthermore, the catalyst demonstrates high stability, which sustained activity over 192 hours of photocatalytic experiment.