Photoinduced Charge Separation Research Articles

Novel Anodic TiO2 Synthesis Method with Embedded Graphene Quantum Dots for Improved Photocatalytic Activity

Photocatalytic degradation of pollutants have a high potential for sustainable and renewable uses. TiO2 is a widely studied photocatalyst due to its high chemical and photochemical stability and wide range of applications. However, the wide band gap and low capacity of photo-induced charge separation provide lower catalytic activity; thus, improvement of these properties must be found. The doping of TiO2 with other elements, such as carbon nanoparticles (CNP) in a quantum dot form, offers a promising pathway to improve the aforementioned properties. In addition, in situ doping methods should be investigated for practical scalability, as they offer the advantage of integrating dopants directly during material synthesis, ensuring a more uniform distribution and better interaction between the dopant and the host material, in turn leading to more consistent photocatalytic properties. Current technologies primarily involve nanoparticle combinations. This work focuses on the development of a novel in situ synthesis methodology by the introduction of three different graphene-based quantum nanodots into anodic TiO2 and the following investigation of structural, morphological, and photocatalytic properties. Results indicate that the introduction of CNP allows for the shift of a set of parameters, such as the optical band gap, increased photo-induced charge carrier density of TiO2/CNP composite, and, most importantly, the change of crystalline phase composition depending on added CNP material. Research indicates that not only a higher concentration of added CNP enhances higher photocatalytic activity as tested by the degradation of methylene blue dye, but also the type of CNP determines final crystalline phase. For the first time brookite and rutile phases were obtained in anodic titania synthesized in inorganic electrolyte by introducing hydrothermally treated exfoliated graphene.

Enhanced photocatalytic performance of TiO2 with tunable oxygen vacancies induced by H2/N2 mixture treatment

Surface treatment can effectively modulate the surface properties of a photocatalyst to hasten the separation and transfer of photoinduced charges, ultimately achieving high photocatalytic performance. Herein, surface treatment of anatase-phase TiO2 prepared by a hydrothermal method was performed under H2/N2 mixed atmosphere. The experimental results demonstrate that roasting TiO2 in a H2/N2 atmosphere can effectively reduce partial Ti4+ to Ti3+, thereby facilitating the production of tunable oxygen vacancies (OVs) by disrupting Ti-O-Ti bonds. OVs can construct defective energy levels to bring about a decrease in the bandgap of TiO2 and an extension of light absorption range. Moreover, OVs remarkedly improve the separation of photoinduced charges of TiO2 and accelerate the photocatalytic reaction as active sites. The photocatalytic experimental results demonstrate that TiO2 exhibits the highest performance when roasting TiO2 in a H2/N2 atmosphere for 2 h, and the photocatalytic degradation rate constant of rhodamine B (RhB) and tetracycline (TC) on this sample under simulated solar light irradiation is 2.24 and 1.11 times higher than that on the reference TiO2, respectively. These findings provide valuable insights for designing highly efficient photocatalysts for effective water pollution treatment.

Fluence-Dependent Photoinduced Charge Transfer Dynamics in Polymer-Wrapped Semiconducting Single-Walled Carbon Nanotubes.

Because an individual single-walled carbon nanotube (SWNT) can absorb multiple photons, the exciton density within a single tube depends upon excitation conditions. In SWNT-based energy conversion systems, interactions between excitons and charges make it possible for multiple types of charge transfer reactions. We exploit a SWNT-molecular donor-acceptor hybrid system (R-PBN(b)-Ph6-PDI-[(6,5) SWNT]) that fixes spatial organization and stoichiometry of perylene diimide (PDI) electron acceptors on the nanotube surface, to elucidate how excitation fluence affects ultrafast charge separation (CS) and the nature of charge recombination (CR) dynamics triggered upon SWNT near-infrared excitation. Pump-probe data characterizing these photoinduced CS and thermal CR reactions were acquired over excitation fluences that produce ∼5-125 excitons per 700 nm long nanotube. These experiments show that optical excitation gives rise to CS states in which PDI radical anions (PDI-•) and SWNT hole polarons (SWNT•+) have geminate and nongeminate spatial relationships. Under low excitation fluences, the observed dynamics reflect CR reactions of these geminate and nongeminate CS states. As excitation fluence increases, persistent excitons, which have not undergone CS, undergo reaction with ([SWNT(•+)n]-(PDI-•)n) CS states to produce lower-energy CS states that are characterized by hole (SWNT•+) and electron (SWNT•-) polarons. When nongeminate SWNT•+ and SWNT•- charge carriers are generated, CR dynamics depend on the time scale required for these oppositely charged solvated SWNT polarons to encounter each other. Because SWNT excitons have substantial excited-state reduction (1E-/*) and excited-state oxidation (1E*/+) potentials, they can drive additional charge transfer reactions involving initially prepared CS states under experimental conditions where excess excitons are present.

Dipole polarization modulating of vinylene-linked covalent organic frameworks for efficient photocatalytic hydrogen evolution

Photocatalytic hydrogen (H2) evolution using covalent organic frameworks (COFs) is an attractive and promising avenue for exploration, but one of its big challenges is low photo-induced charge separation. In this study, we present a straightforward and facile dipole polarization engineering strategy to enhance charge separation efficiency, achieved through atomic modulation (O, S, and Se) of the COF monomer. Our findings demonstrate that incorporating atoms with varying electronegativities into the COF matrix significantly influences the local dipole moment, thereby affecting charge separation efficiency and photostability, which in turn affects the rates of photocatalytic H2 evolution. As a result, the newly developed TMT-BO-COF, which contains highly electronegative O atoms, exhibits the lowest exciton binding energy, the highest efficiency in charge separation and transportation, and the longest lifetime of the active charges. This leads to an impressive average H2 production rate of 23.7 mmol g−1 h−1, which is 2.5 and 24.5 times higher than that of TMT-BS-COF (containing S atoms) and TMT-BSe-COF (containing Se atoms), respectively. A novel photocatalytic hydrogen evolution mechanism based on proton-coupled electron transfer on N in the structure of triazine rings in vinylene-linked COFs is proposed by theoretical calculations. Our findings provide new insights into the design of highly photoactive organic framework materials for H2 evolution and beyond.

Long organic persistent luminescence triggered by photo-induced charge-separation for water-resistant information encryption.

The long persistent luminescence (LPL) phenomenon in the water environment presents us with a broad blueprint to struggle for a new generation of optical materials. However, the realization of water-resistant LPL remains a formidable challenge due to severe quenching of triplet excitons inflowing media. Here, an electron donor-acceptor system is designed based on a B2O3 host and carbon dot (CD) guest, which exhibits deep-blue LPL with a lasting time of about 21 s to the naked eye. The average LPL lifetime is over 2 s, and the LPL quantum yield is 10.78%. This host-guest system possesses charge-separated states and charge-transferred states triggered by an optical source, which is the foundation for LPL. Importantly, in water environments (HCl, NaOH, electrolyte NaCl, and H2O), the LPL of as-obtained CDs@B2O3 can still remain due to high environmental stability of B2O3. Based on the excellent LPL with ultra-long lifetime and water-resistant feature, the CDs@B2O3 successfully applies in water-resistant information encryption.

Efficient and selective photocatalytic oxidation of benzylic alcohols with built-in electric field CsPbBr3/SiO2 nanocomposites through Fe3+ gradient doping

Lead halide perovskite nanocrystals (PNCs) have emerged as promising materials for photocatalysis due to their exceptional optoelectronic properties, yet achieving efficient charge separation and selective oxidation reactions remains a significant challenge. In this study, we report the synthesis of Fe3+-doped CsPbBr3/SiO2 nanocomposites (Fe-PNCs/SNPs) with gradient energy levels, designed to enhance photocatalytic performance. Our results demonstrate that Fe3+ doping introduces mid-gap states, promotes photoinduced charge separation, and generates reactive oxygen species (ROS) such as O2− and OH radicals under sunlight-simulating light irradiation from a 300 W Xe arc lamp. The Fe20-PNCs/SNPs catalyst achieved over 99 % conversion of benzyl alcohol to benzaldehyde with high selectivity and stability in the ethanol under ambient conditions. Additionally, the catalyst exhibited excellent recyclability and broad substrate tolerance. These findings highlight the innovative design of gradient energy levels in perovskite nanocomposites, offering a new strategy for enhancing photocatalytic efficiency in selective organic transformations.

Dual Cocatalysts on Covalent Organic Framework as Charge Transfer Mediator Facilitating Photocatalytic Water Oxidation

AbstractCovalent organic frameworks (COFs) have been regarded as promising photocatalytic materials. However, the sluggish diffusion of photoinduced charges in a single‐component COF remains the obstacles that have to be overcome. Here, we demonstrate a synthesis of a COF bearing dual cocatalysts Co3O4 and Re complex as photocatalyst for water oxidation. The dual cocatalysts are coordinated on the COF, and enable the spatial separation of photoinduced charges. The generated electrons were attracted to Re moiety, while the holes were localized on Co3O4 cocatalyst for water oxidation to produce O2 product. The synergy of dual cocatalysts of COF promote the charge separation and redox reaction. Moreover, hydroxyl radicals generated from the hydration of COF contribute to O−O bond formation, which is the key step of O2 formation. Accordingly, an excellent O2 production rate of 400 μmol g−1 h−1 under visible light irradiation was obtained. This work may pave the way to the development of highly efficient COF photocatalysts for solar energy conversion.

Hollow Nanobox‐Shaped Cu2‐xS@ZnxCd1‐xS Heterojunction by Light Multireflection with Z‐Scheme Mechanism for Enhanced Photocatalytic Hydrogen Production

AbstractAchieving efficient spatial photoinduced charge separation and light utilization for improving the high photocatalytic activity is still a major obstacle. Here, a Cu2‐xS@ZnxCd1‐xS (Cu2‐xS@ZnCdS) heterojunction is reported featuring a distinctive core–shell hollow nanobox structure. The Cu2‐xS@ZnxCd1‐xS exhibits high photocatalytic activity in hydrogen evolution reaction (HER) at the rate of 8175 µmol∙g−1∙h−1 under visible light irradiation, outperforming pristine ZnCdS nanoparticles and Cu2‐xS hollow nanoboxes. The remarkable activity and outstanding stability of Cu2‐x@ZnCdS are attributed to the development of robust interfacial electric fields, and improved light multireflection absorption efficiency as well as the Z‐scheme mechanism. The electron paramagnetic resonance (EPR) and in situ X‐ray photoelectron spectroscopy (XPS) measurements gave the direct evidence of the formation of the Z‐scheme, which maintained the high redox potentials of each ZnCdS and Cu2‐xS. This study gives the guideline for the design of heterojunction with the Z‐scheme mechanism, leading to the high photocatalytic performance and remarkable stability.

Preparation and Photocatalytic Performance of In2O3/Bi2WO6 Type II Heterojunction Composite Materials.

Bismuth-based photocatalytic materials have been widely used in the field of photocatalysis in recent years due to their unique layered structure. However, single bismuth-based photocatalytic materials are greatly limited in their photocatalytic performance due to their poor response to visible light and easy recombination of photogenerated charges. At present, constructing semiconductor heterojunctions is an effective modification method that improves quantum efficiency by promoting the separation of photogenerated electrons and holes. In this study, the successful preparation of an In2O3/Bi2WO6 (In2O3/BWO) II-type semiconductor heterojunction composite material was achieved. XRD characterization was performed to conduct a phase analysis of the samples, SEM and TEM characterization for a morphology analysis of the samples, and DRS and XPS testing for optical property and elemental valence state analyses of the samples. In the II-type semiconductor junction system, photogenerated electrons (e-) on the In2O3 conduction band (CB) migrate to the BWO CB, while holes (h+) on the BWO valence band (VB) transfer to the In2O3 VB, promoting the separation of photoinduced charges, raising the quantum efficiency. When the molar ratio of In2O3/BWO is 2:6, the photocatalytic degradation degree of rhodamine B (RhB) is 59.4% (44.0% for BWO) after 60 min illumination, showing the best photocatalytic activity. After four cycles, the degradation degree of the sample was 54.3%, which is 91.4% of that of the first photocatalytic degradation experiment, indicating that the sample has good reusability. The XRD results of 2:6 In2O3/BWO before and after the cyclic experiments show that the positions and intensities of its diffraction peaks did not change significantly, indicating excellent structural stability. The active species experiment results imply that h+ is the primary species. Additionally, this study proposes a mechanism for the separation, migration, and photocatalysis of photoinduced charges in II-type semiconductor junctions.

Donor-Acceptor Type Supra-Carbon-Dots with Long Lifetime Photogenerated Radicals Boosting Tumor Photodynamic Therapy.

Carbon dots (CDs) have gained significant interest because of their potential in biomedical applications. Nevertheless, developing CDs with efficient photoinduced charge separation for tumor photodynamic therapy (PDT) remains a challenge. This study presents a novel class of supra-carbon-dots (supra-CDs) developed by fusing red emissive CDs with 2,3-dicyanohydroquinone (DCHQ) via post-solvothermal treatment. In supra-CDs, the core, acting as electron donors, is formed by assembled CDs with substantial sp2 domains, the fused interface originating from DCHQ with electron-withdrawing groups functions as the electron acceptor. This configuration creates the unique donor-acceptor nanostructure. Upon white light irradiation, the excited electrons from the assembled CDs were transferred to the electron-withdrawing interface, whereas the photogenerated holes were retained within the assembled CDs as radicals, leading to effective photoinduced charge separation. The separated photogenerated electrons then react with oxygen to generate superoxide radicals. Simultaneously, the photogenerated holes undergo oxidation of crucial cellular substrates. This dual action underscores the exceptional cell-killing efficacy of supra-CDs. Moreover, the increased particle sizes (~20 nm) ensure supra-CDs to exhibit a notable capacity for tumor accumulation via the improved permeability and retention effect, thereby achieving satisfactory anti-tumor PDT efficacy in a mouse subcutaneous tumor model.

Photo-Induced Ultrafast Charge Transfer and Air-Stable Radical Formation in Tetraphenylpyrene Derivatives.

Stable organic radicals generated by photo-excitation hold applications in molecular switching devices and information storage. It remains challenging to develop photo-generated radical materials with rapid response and air stability in the solid state. Here, we report a structure based on 1,3,6,8-tetraphenylpyrene derivative (Py-TTAc) displaying photo-induced radicals with air stability in the solid state. Photo-induced electron transfer, exposed to a 365 nm ultraviolet lamp for 1 minute, affords radicals in Py-TTAc powder as confirmed by electron paramagnetic resonance (EPR) spectroscopy. The maximum radical concentration reaches 2.21 % after continuous irradiation for 1 hour and recurs more than 10 times without any chemical degradation. The mechanistic study according to the femtosecond transient absorption (fsTA) and X-ray technology suggests that the radicals are derived from photo-induced symmetry-breaking charge separation (SB-CS) and stabilized through non-covalent interactions. The photo-generated stable radical system is employed in anti-counterfeiting paper and optoelectronic device applications. This study will provide insights into the development of photoactive organic radical materials.

Nonfullerene Acceptors Bearing Spiro-Substituted Bithiophene Units in Organic Solar Cells: Tuning the Frontier Molecular Orbital Distribution to Reduce Exciton Binding Energy.

The development of nonfullerene acceptors (NFAs), represented by ITIC, has contributed to improving the power conversion efficiency (PCE) of organic solar cells (OSCs). Although tuning the electronic structures to reduce the exciton binding energy (Eb) is considered to promote photocharge generation, a rational molecular design for NFAs has not been established. In this study, we designed and developed two ITIC-based NFAs bearing spiro-substituted bithiophene or biphenyl units (named SpiroT-DCI and SpiroF-DCI) to tune the frontier molecular orbital (FMO) distribution of NFAs. While the highest occupied molecular orbitals (HOMOs) of SpiroF-DCI and ITIC are delocalized in the main π-conjugated framework, the HOMO of SpiroT-DCI is distributed on the bithiophene unit. Reflecting this difference, SpiroT-DCI exhibits a smaller Eb than either SpiroF-DCI or ITIC, and exhibits greater external quantum efficiency in single-component OSCs. Furthermore, SpiroT-DCI shows improved PCEs for bulk-heterojunction OSCs with a donor of PBDB-T, compared with that of either SpiroT-DCI or ITIC. Time-resolved spectroscopy measurements show that the photo-induced intermolecular charge separation is effective even in pristine SpiroT-DCI films. This study highlights the introduction of spiro-substituted bithiophene units that are effective in tuning the FMOs of ITIC, which is desirable for reducing the Eb and improving the PCE in OSCs.

Ultrafast Charge Separation Driven by Solvation-Coupled Intramolecular Torsion.

Photoinduced intramolecular charge separation in a pyrene- and triarylamine-based donor-acceptor dyad was studied by polarization-dependent femtosecond time-resolved transient absorption (TA) spectroscopy in polar solvents. Photoexcitation forms an excited state with charge transfer (CT) character due to the intrinsic electronic coupling between the triarylamine and pyrene groups, resulting in ultrafast charge separation (CS) in polar solvents. TA measurements reveal a correlation between the rate of CS and solvation dynamics, which implies that solvation is involved in the CS reaction. In addition, polarization-dependent TA spectroscopy was devoted to tracking the ultrafast anisotropy evolution of the cationic absorption band, which is attributed to intramolecular torsional motion and is proposed to be coupled to diffusive orientational solvent modes. The results therefore reveal that the evolution of the CT state in the condensed phase is driven by solvation-coupled excited-state structural relaxation. In other words, intramolecular torsional motion is directly confirmed to be involved in the reaction coordinate of the CS reaction in a strongly coupled donor-acceptor dyad.

Photocatalysis with Covalent Organic Frameworks.

ConspectusUtilizing light to enable chemical conversions presents a green and sustainable approach to produce fuels and chemicals, and photocatalysis is one of the key chemical technologies that needs to be well developed in this century. Despite continuous progress in the advancement of various photocatalysts based on small inorganic and organic compounds, polymers, and networks, designing and constructing photocatalysts that combine activity, selectivity, and reusability remains a challenging goal. For catalytic activity, the difficulty originates from the complexity of photochemical reactions, where the light-harvesting system, multielectron and multihole-involving processes, and pinpoint mass delivery simultaneously need to be established in the system. For selectivity, the difficulty stems from the elaborate design of catalytic sites and space, especially their orbital energy levels, spatial arrangement, and environment; developing a molecular strategy that enables an overall design and control of these factors of different aspects is necessary yet arduous. For reusability, the difficulty arises from the stability and recyclability of the photocatalysts upon continuous operation under photoredox reaction conditions. How to recover photocatalysts in an energy-saving way to enable their cyclic use while retaining activity and selectivity is at the core of this problem. These bottleneck issues reflect that molecular design of a photocatalyst is not a simple summation of the above requirements, but a systematic scheme that can organically interlock various aspects is needed.To enable such an elaborate design and precise control, a basic requirement of the scaffold for constructing a promising photocatalyst is that its primary and high-order structures should be molecularly predesignable and synthetically controllable. Such a molecular regime has successfully evolved in natural photosynthesis, where light-harvesting chlorophyll antennae and photocatalytic centers are spatially well-organized and energetically well-defined to build ways for exciton migration, photoinduced electron transfer and charge separation, electron and hole flows, and oxidation of water and reduction of carbon dioxide, thereby converting water into oxygen to release ATP and NADPH via the light reaction and carbon dioxide into glucose with ATP and NADPH through the dark reaction. Similarly, a predesignable polymeric scaffold would be promising for integrating these complex photochemical processes to construct photocatalysts.Covalent organic frameworks (COFs) are a class of extended yet polymeric materials that enable the organization of organic units or metallo-organic moieties into well-defined architectures. In principle, COFs are molecularly designable with topology diagrams and synthetically controllable through polymerization reactions, offering an irreplaceable platform for designing and synthesizing photocatalysts. This feature enticed researchers to develop various photocatalysts based on COFs and drove the rapid progress in this field over the past decade. In this Account, we summarize the recent advances in the molecular design and synthetic control of COF photocatalysts, by highlighting the key achievements in developing ways to enable light harvesting, trigger photoinduced electron transfer and charge separation, allow charge carrier transport and mass delivery, control energy level, catalytic space, and environmental engineering, and develop stability and recyclability with an aim to reveal a full picture of this field. By scrutinizing typical photocatalytic reactions, we show the key problems to be addressed for COFs and predict future directions.

Highly efficient photocatalysis-Fenton degradation of antibiotics and phenol over sulfidated FeOCl under natural sunlight illumination

Sulfidated FeOCl is prepared as a heterogeneous photo-Fenton catalyst. And the surface sulfidation of FeOCl can remarkably accelerate the photoinduced charge separation and transfer, while also increase Fe2+/Fe3+ atomic ratio, leading to the boosted photo-Fenton activity in the presence of H2O2. Under irradiation of natural sunlight (light intensity: ∼80 mW·cm−2), over 10 mg sulfidated FeOCl catalyst with using 20 μL 15 % H2O2, 91.2 % of ofloxacin solution (50 mg·L−1) and 97.5 % of sulfisoxazole solution (60 mg·L−1) can be degraded in 80 min, and 99.6 % of phenol solution (625 mg·L−1) is decomposed in 4 h. Under irradiation of a white Light-Emitting Diode (LED) lamp (light intensity: 5 mW·cm−2), 99.8 % of ofloxacin solution is decomposed after treatment for 4 h. Moreover, this photo-Fenton degradation system displays a stable activity in a wide range of pH (1−10), diverse water bodies, and various coexisting ions with concertation from 1 mM to 500 mM. Moreover, sulfidated FeOCl catalyst coated on a frosted glass sheet exhibits excellent stability for degrading ofloxacin even in seven continuous cycles. Particularly, the non-toxicity of the treated ofloxacin, sulfisoxazole, and phenol solution, have been proven by testing their toxic effects on cabbage seed, bacteria, and human embryonic kidney cell, respectively.

Photoinduced charge separation at heterojunctions between two-dimensional layered materials and small organic molecules.

p-n heterojunctions are fundamental components for electronics and optoelectronics, including diodes, transistors, sensors, and solar cells. Over the past few decades, organic-inorganic p-n heterojunctions have garnered significant interest due to the diverse properties they exhibit, which are a result of the limitless combinations of organic molecules and inorganic materials. This review article concentrates on photoinduced charge separation and photocurrent generation at heterojunctions between two-dimensional layered materials and structurally well-defined organic small molecules. We highlight representative examples, including our work, and critically discuss their potential and perspectives.

Ternary Boron Carbon Nitride nanosheets with improved and controllable linear and nonlinear optical response for efficient photocatalytic performance

This work reports the systematic variation of linear and nonlinear optical (NLO) properties of ternary boron carbon nitride (BCN) nanosheets with varying carbon concentrations. These nanosheets are synthesized by the thermal substitutional method to modulate the band-gap of BCN nanosheets by varying the hBN and graphene domain ratios which is confirmed through UV-Vis absorption spectroscopy. The third-order optical nonlinearity of nanosheets was explored through the Z-scan technique. With increases in both carbon content and laser power, samples' NLO properties have shifted from saturable absorption to reverse saturable absorption. The enhanced nonlinearity with carbon concentration in BCN samples was responsible for higher photoinduced charge separation time. In UV-Vis driven photoreduction of organic pollutants, BCN nanosheets with a decreased bandgap and an increased charge separation time show higher catalytic efficiency. Therefore, based on the combined effect of many processes, the results revealed that the BCN nanosheets displayed greater potential for photoinduced reduction.

Tailoring Light-Harvesting in Zn-Porphyrin and Carbon Fullerene based Donor-Acceptor Complex through Ethynyl-Extended Donor π-Conjugation.

Organic photovoltaic efficiency though currently limited for practical applications, can be improved by means of various molecular-level modifications. Herein the role of extended donor -conjugation through ethynyl-bridged meso-phenyl/pyridyl on the photoinduced charge-transfer kinetics is studied in noncovalently bound Zn-Porphyrin and carbon-fullerene based donor-acceptor complex using time-dependent optimally tuned range-separated hybrid combined with the kinetic rate theory in polar solvent. Noncovalent dispersive interaction is identified to primarily govern the complex stability. Ethynyl-extended -conjugation results in red-shifted donor-localized Q-band with substantially increased dipole oscillator strength and smaller exciton binding energy, suggesting greater light-harvesting efficiency. However, the low-lying charge-transfer state below to the Q-band is relatively less affected by the ethynyl-extended -conjugation, yielding reduced driving forces for the charge-transfer. Detailed kinetics analysis reveals similar order of charge-transfer rate constants (~1012 s-1) for all donor-acceptor composites studied. Importantly, enhanced light-absorption, smaller exciton binding energy and similar charge-transfer rates together with reduced charge-recombination make these complexes suitable for efficient photoinduced charge-separation. These findings will be helpful to molecularly design the advanced organic donor-acceptor blends for energy efficient photovoltaic applications.

In-Situ comparative study of photo-induced charge behavior in single-perovskite Cs3Bi2Br9 and double-perovskite Cs2AgBiBr6

While organic-inorganic lead halide perovskites excel in optoelectronic applications, their use is limited by toxicity and degradation. Consequently, lead-free alternatives like Cs2AgBiBr6, offering greater stability and diverse applications, have been investigated. However, the fundamental structural, optical, and electronic properties of Cs2AgBiBr6 remain insufficiently understood. In this study, we compared the exciton dynamics and photo-induced charge separation in Cs3Bi2Br9 and Cs2AgBiBr6 films using in-situ surface techniques. Both materials display similar surface photovoltage (SPV) peaks in the 450–500 nm range, supporting the hypothesis of Bi 6s-6p orbital transitions in distorted [BiBr6]3− structures. Although many theories propose the presence of self-trapped excitons (STE) in bismuth-based perovskites, sufficient evidence has been lacking. Our observation of a significant redshift in the SPV peak compared to the band edge absorption peak supports STE hypothesis, with Cs2AgBiBr6 showing a more pronounced redshift due to its more complex electronic structure and stronger electron-phonon coupling. Additionally, we observed that Cs2AgBiBr6 exhibits superior charge separation efficiency compared to Cs3Bi2Br9. Notably, Cs2AgBiBr6 shows significantly shorter rise times, indicating more rapid photogenerated charge separation. However, both materials exhibit similar fall times, suggesting comparable charge recombination rates. Light-chopping-frequency dependent SPV measurements further reveal that Cs2AgBiBr6 has a higher charge separation rate than Cs3Bi2Br9. These findings underscore the potential of bismuth-based perovskites for optoelectronic applications and highlight the importance of a comprehensive understanding of their structure-property relationships.

Efficient photocatalytic CO2 and Cr(VI) reduction on carbon spheres/g-C3N4 composites with enriched nitrogen vacancies

In this study, carbon spheres (CS)/g-C3N4 composite materials were fabricated by a hydrothermal method, and the characterizations have confirmed the successful anchoring of CS onto the surface of g-C3N4, constructing enriched nitrogen vacancies during the synthesis process. The photocatalytic CO2 reduction activity of g-C3N4 is enhanced by all of these advantageous factors. The significant enhancement can be attributed to the tight interfacial interaction between CS and g-C3N4, which endows with the photocatalyst a larger specific surface area, higher light utilization efficiency and stronger capability for photoinduced charges separation. Furthermore, the presence of nitrogen vacancies further accelerates the separation and migration efficiency of photogenerated charges, provides additional active sites to promote the adsorption and activation of CO2 molecules, thereby effectively boosting the photocatalytic activity for CO2 reduction. The CO2 conversion rate on CS/g-C3N4 composite materials is higher than that on the reference g-C3N4. The apparent quantum yield (AQY) is also superior to that of the reference g-C3N4 under three different monochromatic light irradiations. The stability of the catalyst was verified through cycling experiments, indicating promising potential practical industrial application. The CO2 reduction mechanism and transformation pathways were elucidated using in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The photocatalytic reduction rate constant of Cr(VI) by 50CS/CN is 2.9 times higher than that by CN. This study introduces a facile approach for synthesizing g-C3N4-based photocatalytic materials, providing an interesting strategy to boost photocatalytic activity of g-C3N4 for photocatalytic CO2 and Cr(VI) reduction.