BiOCl Nanosheets Research Articles

Creating Cation Vacancies in BiOCl Nanosheets Toward Exceptional Visible-Light-Driven Photocatalytic CO2 Reduction.

BiOCl-based materials have emerged as promising photocatalysts for converting CO2 into valuable products and fuels. However, challenges such as low light absorption and inefficient charge carrier separation require effective solutions, with vacancy engineering offering a promising approach. Current research primarily focuses on anion vacancies, leaving cation vacancies less explored. In contrast, this study presents a novel method to enhance visible-light-driven photocatalysts by Bi cation vacancies in ultrathin BiOCl nanosheets through a straightforward hydrochloric acid etching process (HAE-BiOCl). These introduced Bi vacancies not only expand the light absorption range and enhance carrier separation, but also serve as active sites for CO2 adsorption. Additionally, Bi vacancies can effectively lower the activation energy of COOH- species and thereby enhance overall reaction activity. As a result, the HAE-BiOCl catalyst exhibits exceptional photocatalytic CO2 reduction performance without the need for co-catalysts or sacrificial agents. It achieves high CO generation rates of 68.39 and 17.43µmol g-1 h-1 under 300W Xe lamp and visible light irradiation, respectively. These rates are significantly higher compared to counterparts without vacancy creation and surpass those of most reported Bi-based photocatalysts. This study underscores the potential of inducing cation vacancies via acid etching as a valuable strategy for advancing photocatalysis.

Engineering Co Single Atoms in Ultrathin BiOCl Nanosheets for Boosted CO2 Photoreduction

AbstractDespite the development of a range of photocatalysts for CO2 reduction, the practical applications are significantly limited by low conversion efficiencies and their reliance on sacrificial agents, which are rooted in thermodynamic and kinetic challenges related to CO2 conversion. Here, the engineering of Co single atoms in ultrathin single‐crystal BiOCl nanosheets for boosted photocatalytic CO2 reduction is reported. The engineering of Co atoms modulates the distribution of photogenerated charges at the catalyst surface, controlling key surface reaction dynamics and suppressing surface electron‐hole recombination. This modulation also improves light absorption and enhances CO2 adsorption and activation, leading to more efficient surface reactions. Notably, CO2 is stably adsorbed onto the (001) face of BiOCl through a Bi‐O‐C(= O)‐Co‐O coordination unit, which lowers the activation energy for CO2 reduction and reduces the formation energy of COOH− intermediates. As a result, the BiOCl photocatalysts achieve a CO formation rate of 183.9 µmol g−1 h−1, when irradiated with a 300 W Xe lamp without cocatalysts or sacrificial agents. It represents an ≈13‐fold increase compared to that of pristine BiOCl, and surpasses most reported Bi‐based photocatalysts to date. Current work provides valuable insights into engineering of single atoms for developing advanced CO2‐reduction photocatalysts.

Design of CdZnS/BiOCl heterostructure as a highly-efficient piezo-photocatalyst for removal of antibiotic

Facilitating the surface and bulk photocarrier separation in semiconductors is crucially important for enhancing their photocatalytic activities. In this study, we have immobilized CdxZn1−xS (x = 0.7) nanoparticles on the surface of (001)-facet-exposed BiOCl (BOC) nanosheets to form heterostructured CZS/BOC piezo-photocatalysts. Experiments and theories were performed to unveil the piezo-photocatalytic performances of the CZS/BOC heterostructures and involved mechanisms. It is corroborated that the CZS/BOC heterostructures exhibit efficient transfer/separation of photocarriers, and hence possess excellent photocatalysis for eliminating tetracycline hydrochloride (TC). When irradiated by simulated sunlight, the 20 %CZS/BOC heterostructure manifests a photocatalytic activity with η(40 min)/kapp = 95 %/0.06825 min−1, which is enhanced by 6.9 (or 1.9) times over that of bare BOC (or Cd0.7Zn0.3S). While exerting ultrasonic vibration during the simulated-sunlight illumination, i.e., for the piezo-photocatalysis, a further improvement in the TC degradation rate is observed. The synergistic factor is calculated to be 1.5, quantifying the enhancement degree achieved by piezo-photocatalysis collaboration. The enhanced piezo-photocatalysis can be interpreted by the accelerated separation of the bulk photoelectrons and photoholes in the photocatalysts resulted from ultrasonic-induced polarization field, thus elevating their utilization for redox reactions. This work could advance the application of piezo-photocatalysts in environmental remediation.

Needle growth of Nb2O5 nanoparticles on BiOCl nanosheets to fabricate S-scheme heterojunction with oxygen vacancies for enhanced photooxidation of cyclohexane

The exploration of cost-efficient, environmentally friendly, and high-efficacy photocatalysts for the enhanced selective photooxidation of cyclohexane to KA oil (cyclohexanone (CHA-one) and cyclohexanol (CHA-ol)) is a pivotal challenge in the industrial realm. Herein, the present study focuses on the synthesis of needle-like S-scheme heterojunction photocatalysts with oxygen vacancies, which are achieved by the needle growth integration of nano-sized Nb2O5 particles onto the BiOCl nanosheets. Remarkably, the 40 % Nb2O5/BiOCl composites exhibited superior performance in the solvent-free photooxidation of cyclohexane at room-temperature and under atmospheric pressure. The production yield of KA oil was 180.3 μmol (CHA-one/CHA-ol molar ratio = 3.5), and exceptional selectivity towards KA oil, reaching up to 99.3 %. The enhanced photocatalytic efficiency in cyclohexane oxidation can be attributed to the unique S-scheme heterogeneous interfaces with specific nanoneedle morphology, which result in the enhanced photonic absorption, effective charge carrier separation, a high density of oxygen vacancies, and the exposure of the highly reactive (001) plane of BiOCl. The excellent interfacial charge separation and transfer pathways of S-scheme heterojunction are disclosed by the in-depth EPR analysis and DFT calculations. These insights highlight the significant potential of the needle-like Bi-based S-scheme heterojunction photocatalysts for the efficient photooxidation of saturated alkanes.

Doped‐Sn Enhanced the Performance of BiOCl Nanosheet on Electrocatalytic Synthesis of Hydrogen Peroxide

AbstractThe hydrogen peroxide (H2O2) produced through electrochemical two‐electron oxygen reduction reaction (2e− ORR) is a promising green synthesis method and served as potential strategy to replace the energy‐intensive anthraquinone process. Nevertheless, the design of low‐cost and efficient electrocatalysts for 2e− ORR remains a formidable challenge. In this study, Sn‐BiOCl nanosheets electrocatalysts are prepared for expediting the 2e− ORR, achieving a high H2O2 selectivity of 92.9%, and the H2O2 yield of 10628 mg L−1 h−1 (0.1 mg cm−2) in a flow‐cell device. The in situ ATR‐SEIRAS results reveal that Sn‐BiOCl enhances the adsorption and activation of *OOH compared to BiOCl, resulting in higher activity and selectivity for 2e− ORR. Furthermore, this study investigates the potential for on‐site production and application of H2O2 using Sn‐BiOCl, which displays a 95% degradation removal of dyes (RhB, MB, and MO) within 20 min. This work not only have an insight into the critical roles of Bi and Sn atoms in enhancing the catalytic performance but also provides a thought to design efficient catalysts for production H2O2 via electrochemical 2e− ORR.

Highly‐Sensitive and High Operating Range Fully‐Printed Humidity Sensors Based on BiFeO3/BiOCl Heterojunctions

AbstractFully‐printed humidity sensors based on BiFeO3/BiOCl heterojunctions fabricated using a two‐step process with serigraphic printing are reported. Most importantly, this unique sensor architecture provides a broader relative humidity sensing range compared to pristine BFO sensors due to a synergistic effect between dense networks of BiOCl nanosheets synthetized atop BFO powders. With surface‐to‐weight ratios reaching 7.75 m2 g−1, these heterostructures increase the sensitivity and operating range of BFO‐based humidity sensors. While previously reported BFO humidity sensors only detect relative humidities above 30%, The BFO/BiOCl heterojunctions can measure relative humidities as low as 15% due to their increased surface area. Optimal growth and packing of the BiOCl nanosheet/BFO powder heterostructure are achieved by tuning the loading of the BFO powder and simultaneously forming the BiOCl sheets by chemical etching and annealing of the BFO powder. Excellent performance of optimized sensors including tracking and monitoring different types of breathing are demonstrated while mounted on an oxygen mask.

Boosted antibiotic elimination over 2D/2D mesoporous CeO2/BiOCl S-scheme photocatalyst

Exploring efficient photocatalysts holds significant importance for the prevention and treatment of antibiotic pollution. This research reports a 2D/2D CeO2/BiOCl S-scheme photocatalyst constructed by mesoporous CeO2 and BiOCl nanosheets (NSs). Efficient charge separation and transfer was achieved by the synergistic effect of large-area contact and S-scheme charge transfer mechanism, which significantly enhanced the photocatalytic performance of CeO2/BiOCl. Experimental results demonstrated that the CeO2/BiOCl photocatalyst displayed superior photocatalytic activity to the individual components, which could efficiently eliminate four types of antibiotics, namely tetracycline (TC), chlortetracycline (CTC), doxycycline (DOC), and oxytetracycline (OTC) under UV light irradiation. Particularly, the sample of 0.4CeO2/BiOCl exhibited the highest catalytic efficiency, with a TC degradation rate constant of 0.01524 min−1, which was 1.85 and 22.74 times higher than that of single CeO2 and BiOCl, respectively. Moreover, liquid chromatograph-mass spectrometer (LC-MS) analysis is employed to reveal the degradation pathways of TC. This work offers an insightful idea for the fabrication of novel S-scheme photocatalysts applied in environmental purification.

Synthesis of strongly interactive FeWO4/BiOCl heterostructures for efficient photoreduction of CO2 and piezo-photodegradation of bisphenol A

Development of multi-functional photocatalysts for CO2 reduction and pollutant elimination is practically significant for solving the environmental problems and energy shortages. In this study, we have immobilized FeWO4 (FWO) nanoparticles on the surface of (001)-facet-exposed BiOCl (BOC) nanosheets through their strong electrostatic interaction to form FWO/BOC heterojunctions. Experimental and theoretical studies corroborate that the FWO/BOC heterojunctions exhibit high-efficiency Z-scheme transfer and separation of photocarriers, and possess excellent photocatalysis for CO2 reduction and bisphenol A (BPA) degradation. Under simulated-sunlight irradiation, the 9 %FWO/BOC heterojunction exhibits a photoreduction performance with CH4/CO yield rates of 4.25/9.41 μmol g−1 h−1 (5 h reaction), which are 3.86/5.26 times higher than those for bare BOC; whereas its photodegradation performance (η(60 min) = 66.8 %, kapp = 0.01755 min−1) is enhanced by 4.3 and 2.7 times compared with that of bare FWO and BOC, respectively. Furthermore, when ultrasonic vibration is simultaneously employed during the simulated-sunlight illumination, the ultrasonic-induced piezoelectric polarization field in BOC nanosheets accelerates the bulk photocarrier separation, resulting in a further improvement in the BPA degradation, and the calculated SF = 1.79 quantifies the degree of enhancement achieved by piezo-photocatalysis collaboration. The introduction of a moderate amount of H2O2 or peroxymonosulfate (PMS) in the reaction solution plays a significant role in promoting the BPA degradation due to the generation of additional •OH and •SO4− reactive species. The mechanisms for photocatalytic CO2 reduction and piezo-photodegradation of BPA catalysis were deeply studied by combining experiments and theory.

Solar Light-Driven Molecular Oxygen Activation by BiOCl Nanosheets: Synergy of Coexposed {001}, {110} Facets and Oxygen Vacancies.

Single-crystalline BiOCl nanosheets with coexposed {001} and {110} facets, as well as oxygen vacancies, were synthesized using a simple method. These nanosheets have the ability to activate molecular oxygen, producing reactive superoxide radicals (77.8%) and singlet oxygen (22.2%) when exposed to solar light. The BiOCl demonstrated excellent photocatalytic efficiency in producing H2O2 under simulated solar light and in oxidatively hydroxylating phenylboronic acid under blue LED light. Our research highlights the significance of constructing coexposed {001} and {110} facets, as well as oxygen vacancies, in enhancing photocatalytic performance. The BiOCl nanosheets have the capability to produce H2O2 with a solar-to-chemical energy conversion efficiency of 0.11%.

Construction of polarized 2D/2D g-C3N4/BiOCl nanosheet dual piezoelectric Z-scheme heterojunction and its efficient charge separation mechanism

A multi-electric field synergistic strategy based on heterojunction construction and polarization engineering enhances carrier separation and migration, achieving excellent piezoelectric photocatalytic performance of g-C3N4 based materials. Here, through the in-situ growth of BiOCl nanosheets (BOCs) on g-C3N4 nanosheets (GCNs), a 2D/2D Z-scheme GCNs/BOCs heterojunction was successfully fabricated, and its outstanding piezo-photocatalytic property was demonstrated. Compared to individual BOCs and GCNs, the high degradation rate (97.64 %) of rhodamine B (RhB) can be achieved over the optimal composite (GCNs/BOCs-50) after 50 min irradiation. Inspiringly, the polarized GCNs/BOCs-50 composite degraded RhB almost completely within 30 min under the simultaneous light irradiation and ultrasound, which reduced the photocatalytic time by 40 %, and its k reached 0.1410 min−1 (12.59 and 2.48 times that of BOCs and GCNs). This work is of great significance for designing a novel heterojunction photocatalysts using polarized ferroelectric materials.

Preparation and photocatalytic performance of BiOCl nanosheet–TiO2 nanotube array composites

Combining BiOCl with TiO2 nanomaterials is beneficial to enhance the photocatalytic activity and optoelectronic activity. In this paper, BiOCl nanosheet–TiO2 nanotube array composites were synthesized to enhance the photocatalytic degradation performance for methyl orange (MO) of TiO2 under ultraviolet light irradiation. BiOCl nanosheets were deposited on TiO2 nanotube arrays by the straightforward impregnation method. X-ray diffraction, scanning electron microscopy, energy dispersive x-ray spectroscopy, transmission electron microscopy, x-ray photoelectron spectroscopy, and photocurrent (i–t) were used to evaluate the composites of BiOCl nanosheets–TiO2 nanotube arrays. The results showed that the tetragonal BiOCl nanosheets clustered together on the surface of the TiO2 nanotubes and grew along the (110) crystal plane. The composites outperformed pure TiO2 regarding outstanding structure and overall photocatalytic performance, and the MO photocatalytic degradation rate was 98.5%. For the 30-BiOCl–TiO2, its photocurrent intensity (58 µA) was 4.5 higher than TiO2 (13 µA). The degradation rate of 87% can still be reached after three cycles.

Oxygen Vacancy Piezoelectric Nanosheets Constructed by a Photoetching Strategy for Ultrasound "Unlocked" Tumor Synergistic Therapy.

Piezoelectric dynamic therapy (PzDT) is an effective method of tumor treatment by using piezoelectric polarization to generate reactive oxygen species. In this paper, two-dimensional Cu-doped BiOCl nanosheets with surface vacancies are produced by the photoetching strategy. Under ultrasound, a built-in electric field is generated to promote the electron and hole separation. The separated carriers achieve O2 reduction and GSH oxidation, inducing oxidative stress. The bandgap of BiOCl is narrowed by introducing surface oxygen vacancies, which act as charge traps and facilitate the electron and hole separation. Meanwhile, Cu doping induces chemodynamic therapy and depletes GSH via the transformation from Cu(II) to Cu(I). Both in vivo and in vitro results confirmed that oxidative stress can be enhanced by exogenous ultrasound stimulation, which can cause severe damage to tumor cells. This work emphasizes the efficient strategy of doping engineering and defect engineering for US-activated PzDT under exogenous stimulation.

Synthesis of a 3D Flower-Like BiOCl/Bi-MOF Heterostructure for High-Performance Removal of Rhodamine B and Tetracycline Hydrochloride.

Semiconductor materials based on bismuth metal have been extensively explored for their potential in photocatalytic applications owing to their distinctive crystal structure. Herein, we present the development of a hybrid photocatalyst, CAU-17/BiOCl, featuring a flower-like nanosheet morphology tailored for the photocatalytic degradation of organic contaminants such as rhodamine B (RhB) and tetracycline hydrochloride (TCH). The composite material is obtained by growing thin CAU-17 layers directly onto the host flower-like BiOCl nanosheets under solvothermal conditions. The optimized CAU-17/BiOCl composite possesses excellent photocatalytic performance, achieving a notable 96.0% removal rate for RhB and 78.4% for TCH after 60 and 90 min of LED light irradiation, respectively. This boosted activity is attributed to the heightened absorption of visible light caused by BiOCl and the provision of additional reaction sites due to the thin CAU-17 layers. Furthermore, the establishment of an S-scheme heterojunction mechanism enables efficient charge separation between CAU-17 and BiOCl, facilitating the separation of photoinduced electrons (e-) and holes (h+). Analysis of the degradation mechanism of RhB and TCH reveals the predominant role of superoxide radicals (•O2-), e-, and h+ in the photocatalytic degradation process. Moreover, the removal efficiency of TCH can reach approximately 64.5% after four cycles of recycling of CAU-17/BiOCl. Our work provides a facile, effective solution and a theoretically explained approach for the effective degradation of pollutants using heterojunction photocatalysts.

Surface hydroxyl manipulation of BiOCl nanosheets for promoted O2 activation and photocatalytic NO removal

Surface hydroxyl manipulation of BiOCl nanosheets for promoted O2 activation and photocatalytic NO removal

High capacity and long service in sodium-ion batteries achieved by the refinement of BiOCl from lamellar to flower-like in ether electrolyte

Sodium-ion batteries (SIBs) have emerged as a promising contender in power systems owing to their cost-effectiveness and safety advantages. However, alloy-type anode materials, crucial for SIB performance, often face challenges such as significant volume expansion and rapid capacity decay at high current densities. In this study, an ion-exchange strategy is used to fabricate ultra-thin and porous BiOCl nanosheets (UTP BiOCl NS) as an anode material for SIB. Remarkably, lamellar UTP BiOCl NSs can transform a flower-like shape in ether electrolytes. This structural change is beneficial in shortening the Na+ transport path, which facilitates rapid electrolyte entry and enhances the dynamic behavior of SIBs. Electrochemically, UTP BiOCl NS demonstrates an exceptional capacity of 212.4 mAh/g and high service stability of up to 3000 cycles at a high current density of 5 A/g, showcasing exceptional durability and promising application potential. Furthermore, the SIB full-cell, coupled with a Na3V2(PO4)3 cathode and UTP BiOCl NS anode, enables an outstanding sodium storage capacity of 140.5 mAh/g and powers a 3 W bulb. This research provides a strategic approach for identifying suitable SIB anodes and aims to inspire researchers to focus on advancing anode materials in SIBs.

Boosting Visible-Light Photocatalytic Activity of BiOCl Nanosheets via Synergetic Effect of Oxygen Vacancy Engineering and Graphene Quantum Dots-Sensitization.

In recent years, oxygen vacancy (VO) engineering has become a research hotspot in the field of photocatalysis. Herein, an efficient GQDs/BiOCl-VO heterojunction photocatalyst was fabricated by loading graphene quantum dots (GQDs) onto BiOCl nanosheets containing oxygen vacancies. ESR and XPS characterizations confirmed the formation of oxygen vacancy. Combining experimental analysis and DFT calculations, it was found that oxygen vacancy promoted the chemical adsorption of O2, while GQDs accelerated electron transfer. Benefiting from the synergistic effect of oxygen vacancy, GQDs, and dye sensitization, the as-prepared GQDs/BiOCl-VO sample exhibited improved efficiency for RhB degradation under visible-light irradiation. A 2 wt% GQDs/BiOCl-VO composite effectively degraded 98% of RhB within 20 min. The main active species were proven to be hole (h+) and superoxide radical (·O2-) via ESR analysis and radical trapping experiments. This study provided new insights into the effective removal of organic pollutants from water by combining defect engineering and quantum dot doping techniques in heterojunction catalysts.

Highly efficient visible-light driven dye degradation via 0D BiVO4 nanoparticles/2D BiOCl nanosheets p-n heterojunctions

The construction of hybrid heterojunction photocatalysts is an effective strategy to improve the utilization of photogenerated carriers and photocatalytic activity. To enhance the separation distance of photogenerated carriers and accelerate the effective separation at the heterojunction of the interface, a unique 0D-2D hierarchical nanostructured p-n heterojunction was successfully fabricated in this work. BiOCl (BOC) nanosheets (p-type) were in situ grown on BiVO4 (BVO) nanoparticles (n-type) using the microemulsion-calcination method for highly efficient visible-light-driven organic dye degradation. Compared with pure BVO (the degradation rate of rhodamine B (RhB): about 32.0% in 55 min, the mineralization rate: 24.9% in 120 min), the RhB degradation rate can reach about 99.5% in 55 min and the mineralization rate of 62.1% in 120 min by utilizing BVO/25%BOC heterojunction photocatalyst under visible light irradiation. Various characterizations demonstrate that the formation of BVO/BOC p-n heterojunction greatly facilitates photogenerated carriers separation efficiency. Meanwhile, the results of the scavenging experiments and electron spin resonance tests indicate that ·O2− and h+ are the prominent active species for Rh B degradation. In addition, possible degradation pathways for Rh B were proposed using LC-MS tests. This work proves that building low dimensional p-n heterojunction photocatalysts is a promising strategy for developing photocatalysts with high efficiency.

One-step synthesis of BiOCl/Bi4NbO8Cl heterostructures with high-purity and enhanced photocatalytic activities via in-situ room-temperature acid-etching

In this study, BiOCl/Bi4NbO8Cl heterojunctions with improved photocatalytic performance were designed and synthesized by in-situ room-temperature acid-etching. Bi4NbO8Cl prepared by the solid-phase method was often accompanied by certain impurities, such as Bi24O31Cl10 and Bi3NbO7. With the assistance of glacial acetic acid, the impurities could be eliminated. At the same time, BiOCl nanosheets were formed in situ at room temperature, and BiOCl/Bi4NbO8Cl (BBN) heterostructures were obtained. For comparison, pure Bi4NbO8Cl was prepared using the molten salt method (S-BNC). Compared to S-BNC, BBN exhibited better performance in degrading rhodamine B (RhB) and ciprofloxacin (CIP). The mechanism of the improved photocatalytic activities was studied by analyzing photoluminescence spectra, UV–vis diffuse reflection absorption spectra, and cyclic voltammetry curves.

Elevating the Photocatalytic Performance of BiOCl by Promoting Light Utilization: From Co doping to the Microreactor.

Owing to its unique layered structure, BiOCl demonstrates high photocatalytic activity. However, its wide bandgap hinders the absorption of visible light. Doping modification is an effective method to expand the light absorption edge of photocatalysts by creating a doping energy level within the bandgap. Herein, Co as a variable valence element was used to dope the BiOCl nanosheets through a simple hydrothermal approach. As a result, the absorption edge of Co-BiOCl extends to the visible light region, and the photocatalytic performance was enhanced by 3.02 times. To overcome the shortcoming of photons being consumed easily in the bulk reactor, a planar microreactor was introduced to reduce the attenuation of light and accelerate the mass transfer. By comparison to the bulk reactor, a maximum of 15.3-fold additional activity promotion emerged. This work combines doping modification and reactor improvement to realize highly efficient photocatalysis in practical application.

A flower-like heterojunction for highly photocatalytic treating oxytetracycline based on chrome-based metal-organic frameworks decorated BiOCl nanosheet

The widespread use of antibiotics poses significant risks to both human health and the environment. Among various approaches, photocatalysis has emerged as a promising method for addressing the issue of antibiotic residues. BiOCl, a semiconductor photocatalyst, has attracted attention due to its distinctive structure. However, the limited light utilization efficiency of its ultraviolet light responsiveness remains a challenge. In this study, we developed a heterojunction by decorating BiOCl with metal-organic frameworks (MOFs) MIL-100(Cr), referred to MIL-100(Cr)/BiOCl (MB), to efficiently treat the antibiotic oxytetracycline (OTC) under visible light irradiation. Various analytical techniques, including X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and scanning electron microscopy, were used to verify the formation of the MB heterojunction. The interaction between MIL-100(Cr) and BiOCl in the MB heterojunction substantially enhances the responsiveness to visible light, increases the specific surface area, facilitates the separation and transfer of charged carriers, and ultimately results in a significant enhancement in visible light-driven photocatalytic performance for OTC degradation. This study explores the application of narrow/wide band gap nanomaterials-based nanocomposites in environmental remediation by constructing heterojunctions.