RESUMEN
Visible-light-driven N2 reduction into NH3 in pure H2O provides an energy-saving alternative to the Haber-Bosch process for ammonia synthesizing. However, the thermodynamic stability of N≡N and low water solubility of N2 remain the key bottlenecks. Here, we propose a solution by developing a WO3-x hollow sphere with oxygen vacancies. Experimental analysis reveals that the hollow sphere structure greatly promotes the enrichment of N2 molecules in the inner cavity and facilitates the chemisorption of N2 onto WO3-x-HS. The outer layer's thin shell facilitates the photogenerated charge transfer and the full exposure of O vacancies as active sites. O vacancies exposed on the surface accelerate the activation of N≡N triple bonds. As such, the optimized catalyst shows a NH3 generation rate of 140.08 µmol g-1 h-1, which is 7.94 times higher than the counterpart WO3-bulk.
RESUMEN
The construction of heterojunctions has been used to optimize photocatalyst fuel denitrification. In this work, HKUST-1(Cu) was used as a sacrificial template to synthesize a composite material CuxO (CuO/Cu2O) that retains the original MOF framework for photocatalytic fuel denitrification by calcination at different temperatures. By adjusting the temperature, the content of CuO/Cu2O can be changed to control the performance and structure of CuxO-T effectively. The results show that CuxO-300 has the best photocatalytic performance, and its denitrification rate reaches 81% after 4 hours of visible light (≥420 nm) irradiation. Through the experimental analysis of pyridine's infrared and XPS spectra, we found that calcination produces CuxO-T mixed-valence metal oxide, which can create more exposed Lewis acid sites in the HKUST-1(Cu) framework. This leads to improved pyridine adsorption capabilities. The mixed-valence metal oxide forms a type II semiconductor heterojunction, which accelerates carrier separation and promotes photocatalytic activity for pyridine denitrification.
RESUMEN
The rapid recombination of charge carriers in semiconductor-based photocatalysts results in a low photocatalytic activity. Co-catalysis is considered a promising strategy to improve the photocatalytic performance of semiconductors. In this study, a bimetallic phosphide was grown by a facile in situ growth method. Loading the cocatalyst (7 wt% NiCoP) leads to activity enhancement by a factor of approximately 27 times in the visible-light-driven hydrogen evolution relative to the pristine Zn0.5Cd0.5S. The photocatalysis shows a high hydrogen evolution rate of 19.5 mmol g-1 h-1, which is much higher than that of the single metal phosphide (Ni2P: 7.0 mmol g-1 h-1; CoxP: 8.1 mmol g-1 h-1) and 7 wt% Pt modified Zn0.5Cd0.5S (0.3 mmol g-1 h-1). Its apparent quantum efficiency reaches 41.6% at 420 nm. Moreover, the photocatalyst exhibits a remarkable photostability for five consecutive cycles of photocatalytic activity measurements with a total reaction time of 15 hours. The excellent photocatalytic activity of the photocatalyst was attributed to the in situ-formed NiCoP cocatalyst, which not only acts as a reactive site but also accelerates the separation of charge carriers.
RESUMEN
Designing frustrated Lewis pair (FLP)-structured photocatalysts is a new challenge in catalysis. In particular, the relationship between the active sites and photocatalytic charge transport mechanism over FLP-structured photocatalysts is still ill-defined. In this study, a novel perylene-3,4,9,10-tetracarboxylic diimide/UiO-66(Ti/Zr)-NH2 (denoted as PDI/TUZr) photocatalyst is successfully constructed using an ammoniation process. The PDI/TUZr heterojunction is equipped with a unique "Zr/Ti SBUs-ligand-PDI" FLP structure and exhibits remarkable catalytic FLP properties. In this "Zr/Ti SBUs-ligand-PDI" structure, the Zr/Ti bimetal centers and PDI serve as Lewis acid and base sites, respectively, and the C-N chemical bond provides a channel for electron transmission, and a bimetallic system facilitates electron transfer from excited ligand to Zr/Ti-SBUs nodes. These superior microstructural designs cooperate to promote substrate activation for photocatalytic antibacterial reactions. Accordingly, 2.2-fold enhancement is achieved in visible photocatalytic antibacterial activity on Staphylococcus aureus for 4%PDI/0.2TUZr composite compared with unadorned UZr. This study provides insights into the formation and carrier transfer behaviors of solid FLP on MOFs and illustrates a rational strategy for the construction of highly efficient photocatalysts.
RESUMEN
Developing novel photocatalysts with an intimate interface and sufficient contact is significant for the separation and migration of photogenerated carriers. In this work, a novel Co@NC/ZnIn2S4 heterojunction with a strong Co-S chemical bond was formed at the interface between Co@NC and ZnIn2S4, which accelerated charge separation. Meanwhile, the recombination of the electron-hole pairs was further restricted by the Co@NC/ZnIn2S4 Schottky junction. The Co@NC (5 wt%)/ZnIn2S4 composite exhibited an H2 evolution rate of 33.3 µmol h-1, which is 6.1 times higher than that of the pristine ZnIn2S4, and Co@NC/ZnIn2S4 showed excellent stability in the photocatalytic water splitting reaction. Its apparent quantum yield reached 38% at 420 nm. Furthermore, the Kelvin probe test results showed that the interfacial electric field formed as the driving force for interface charge transfer was oriented from Co@NC to ZnIn2S4. In addition, the Co-S bond as a high-speed channel facilitated the interfacial electron transfer. This work reveals that in situ formed chemical bonds will pave the way for designing high-efficiency heterojunction photocatalysts.
RESUMEN
Knowledge of the photocatalytic H2-evolution mechanism is of critical importance for water splitting, and for designing active catalysts for a sustainable energy supply. In this study, we prepared plasmon Au-modified K-doped defective graphitic carbon nitride (Au/KCNx) and then applied it in photocatalytic hydrogen-production tests. The hydrogen-production rate of the Au/KCNx photocatalyst (8.85 mmol g-1 h-1) was found to be almost 104 times higher than that of Au/g-C3N4 (0.085 mmol g-1 h-1), together with an apparent quantum efficiency of 12.8% at 420 nm. It could significantly improve the photocatalytic activities of the Au/KCNx sample, which was attributed to the synergistic effects of the plasmon effect, potassium doping, and nitrogen vacancy. In addition, the Au/KCNx photocatalyst had a large surface area, which was beneficial for photogenerated carrier separation and transfer. The novel strategy proposed here is a potential new method for the development of graphitic carbon nitride photocatalysts with obviously enhanced activities.
RESUMEN
The rapid recombination of photogenerated carriers and strong photocorrosion have considerably limited the practical application of CdS in the field of photocatalysis. Loading a cocatalyst has been widely utilized to largely enhance photocatalytic activity. In the present work, a WC@C cocatalyst was prepared by a novel molten salt method and explored as an efficient noble-metal-free cocatalyst to significantly enhance the photocatalytic hydrogen evolution rate of CdS nanorods. The WC@C/CdS composite photocatalyst with a 7 wt% content of WC@C showed the highest photocatalytic hydrogen evolution rate of 8.84 mmol g-1 h-1, which was about 21 and 31 times higher than those of CdS and 7 wt% Pt/CdS under visible light irradiation. A high apparent quantum efficiency (AQY) of 55.28% could be achieved under 420 nm monochromatic light. Furthermore, the photocatalytic activity of the 7 wt% WC@C/CdS photocatalyst exhibited good stability for 12 consecutive cycles of the photocatalytic experiment with a total reaction time of 42 h. The excellent photocatalytic performance of the photocatalyst was attributed to the formation of a Schottky junction and the loading cocatalyst, which not only accelerated the separation of the photogenerated carrier but also provided a reactive site for hydrogen evolution. This work revealed that WC@C could act as an excellent cocatalyst for enhancing the photocatalytic activity of CdS nanorods.
RESUMEN
The enhancement of photogenerated carrier separation efficiency is a significant factor in the improvement of photocatalyst performance in photocatalytic hydrogen evolution. Heteroatom doping and defect construction have been considered valid methods to boost the photocatalytic activity of graphitic carbon nitride. Herein, we report graphitic carbon nitride modified with P doping and N defects (PCNx), and the effects of doping and defects were investigated in photocatalytic H2 evolution. Its hydrogen evolution rate can reach up to about 59.1 µmol h-1, which is more than 123.1 times higher than pristine graphitic carbon nitride under visible light irradiation. Importantly, the apparent quantum efficiency reaches 8.73% at 420 nm. The excellent performance of the PCNx photocatalyst was attributed to the following aspects: (I) the large BET surface area of PCNx affords more active sites for H2 production and (II) the introduction of P and N defects can accelerate the charge carrier separation and transfer efficiency, leading to more efficient photocatalytic hydrogen production. The photocatalyst showed obviously enhanced activities.
RESUMEN
The construction of a multi-component heterostructure for promoting the exciton splitting and charge separation of conjugated polymer semiconductors has attracted increasing attention in view of improving their photocatalytic activity. Here, we integrated Au nanoparticles (NPs) decorated CeO2 (Au-CeO2) with polymeric carbon nitride (PCN) via a modified thermal polymerization method. The combination of the interfacial interaction between PCN and CeO2 via N-O or C-O bonds, with the interior electronic transmission channel built by the decoration of Au NPs at the interface between CeO2 and PCN, endows CeAu-CN with excellent efficiency in the transfer and separation of photo-induced carriers, leading to the enhancement of photochemical activity. The amount-optimized CeAu-CN nanocomposites are capable of producing ca. 80 µmol· H2 per hour under visible light irradiation, which is higher than that of pristine CN, Ce-CN and physical mixed CeAu and PCN systems. In addition, the photocatalytic activity of CeAu-CN remains unchanged for four runs in 4 h. The present work not only provides a sample and feasible strategy to synthesize highly efficient organic polymer composites containing metal-assisted heterojunction photocatalysts, but also opens up a new avenue for the rational design and synthesis of potentially efficient PCN-based materials for efficient hydrogen evolution.
RESUMEN
Effective design of photocatalysts is an effective method to improve the separation of photogenerated carriers, which improves the photocatalytic performance of photocatalysts. In this work, CoCu-ZIF materials with bimetallic structure were synthesized at room temperature for efficient photocatalytic fuel denitrification. The properties and structures of CoCu-ZIF photocatalysts can be effectively controlled by adjusting the molar ratio of cobalt to copper. The as-prepared CoCu-ZIF photocatalysts were characterized by XRD, FT-IR, SEM, TEM, UV-vis, Raman, BET and other techniques. The photoactivity of CoCu-ZIF for the denitrogenation of NCCs has been evaluated using visible light (λ ≥ 420 nm). The results indicate that Co8Cu2-ZIF photocatalysts exhibit excellent photocatalytic properties, in which the denitrification rate almost reached 80% after 4 hours under visible light irradiation, which is higher than the degradation ability of ZIF-67 (38%). Transient photoelectrochemical experiments and EIS Nyquist plots indicate that Co8Cu2-ZIF with unique structure efficiently improves the separation and transfer of photogenerated electron-hole pairs. Moreover, a possible reaction mechanism was proposed by LC-MS analysis.
RESUMEN
Effectively reducing the concentration of nitrogen-containing compounds (NCCs) remains a significant but challenging task in environmental restoration. In this work, a novel step-scheme (S-scheme) SnO2@MCr heterojunction was successfully fabricated via a facile hydrothermal method. At this heterojunction, MIL-101(Cr) octahedrons are decorated with highly dispersed SnO2 quantum dots (QDs, approximate size 3 nm). The QDs are evenly wrapped around the MIL-101(Cr), forming an intriguing zero-dimensional/three-dimensional (0D/3D) S-scheme heterostructure. Under simulated sunlight irradiation (280 nm < λ < 980 nm), SnO2@MCr demonstrated superior photoactivity toward the denitrification of pyridine, a typical NCC. The adsorption capacity and adsorption site of SnO2@MCr were also investigated. Tests using 20%SnO2@MCr exhibited much higher activity than that of pure SnO2 and MIL-101(Cr); the reduction ratio of Cr(VI) is rapidly increased to 95% after sunlight irradiation for 4 h. The improvement in the photocatalytic activity is attributed to (i) the high dispersion of SnO2 QDs, (ii) the binding of the rich adsorption sites with pyridine molecules, and (iii) the formation of the S-scheme heterojunction between SnO2 and MIL-101(Cr). Finally, the photocatalytic mechanism of pyridine was elucidated, and the possible intermediate products and degradation pathways were discussed.
RESUMEN
The design and synthesis of a Z-schematic photocatalytic heterostructure with an intimate interface is of great significance for the migration and separation of photogenerated charge carriers, but still remains a challenge. Here, we developed an efficient Z-scheme organic/inorganic g-C3N4/LDH heterojunction by in situ growing of inorganic CoAl-LDH firmly on organic g-C3N4 nanosheet (NS). Benefiting from the two-dimensional (2D) morphology and the surface exposed pyridine-like nitrogen atoms, the g-C3N4 NS offers efficient trap sits to capture transition metal ions. As such, CoAl-LDH NS can be tightly attached onto the g-C3N4 NS, forming a strong interaction between CoAl-LDH and g-C3N4 via nitrogen-metal bonds. Moreover, the 2D/2D interface provides a high-speed channel for the interfacial charge transfer. As a result, the prepared heterojunction composite exhibits a greatly improved photocatalytic H2 evolution activity, as well as considerable stability. Under visible light irradiation of 4 h, the optimal H2 evolution rate reaches 1952.9 µmol g-1, which is 8.4 times of the bare g-C3N4 NS. The in situ construction of organic/inorganic heterojunction with a chemical-bonded interface may provide guidance for the designing of high-performance heterostructure photocatalysts.
RESUMEN
The difficulty of adsorption and activation of CO2 at the catalytic site and rapid recombination of photogenerated charge carriers severely restrict the CO2 conversion efficiency. Here, we fabricate a novel alkaline Co(OH)2-decorated ultrathin 2D titanic acid nanosheet (H2Ti6O13) catalyst, which rationally couples the structural and functional merits of ultrathin 2D supports with catalytically active Co species. Alkaline Co(OH)2 beneficially binds and activates CO2 molecules, while monolayer H2Ti6O13 acts as an electron relay that bridges a photosensitizer with Co(OH)2 catalytic sites. As such, photoexcited charges can be efficiently channeled from light absorbers to activated CO2 molecules through the ultrathin hybrid Co(OH)2/H2Ti6O13 composite, thereby producing syngas (CO/H2 mixture) from photoreduction of CO2. High evolution rates of 56.5 µmol h-1 for CO and 59.3 µmol h-1 for H2 are achieved over optimal Co(OH)2/H2Ti6O13 by visible light illumination. In addition, the CO/H2 ratio can be facilely tuned from 1:1 to 1:2.4 by changing the Co(OH)2 content, thus presenting a feasible approach to controllably synthesize different H2/CO mixtures for target applications.
RESUMEN
In this work, a novel step-scheme (S-scheme) Bi2MoO6/CdS heterojunction (HJ) photocatalyst (PC) was successfully prepared by a two-step solvothermal method for the first time. One-dimensional CdS nanorods were prepared by a simple solvothermal method as a synthesis template. Then, a Bi2MoO6 precursor was added to obtain a series of Bi2MoO6/CdS HJ composite catalytic materials with different morphologies. The photocatalytic performance of the catalyst was investigated by simulating fuel denitration as a probe reaction under visible light excitation (>420 nm). When compared with pure Bi2MoO6 and CdS, the 0.65-Bi2MoO6/CdS composite shows the highest photocatalytic activity for pyridine degradation. Degradation of pyridine reached 81% after 240 min of visible light excitation. The degradation rate of 0.65-Bi2MoO6/CdS reached 0.4471 h-1, which was 1.8 and 3.2 times higher than that of CdS (0.2493 h-1) and Bi2MoO6 (0.1427 h-1), respectively. Combined with a series of characterisation results, the improvement in pyridine degradation activity was mainly attributed to (1) the S-scheme HJ structure between Bi2MoO6 and CdS, which greatly promoted the separation of photogenerated electrons and holes while retaining its strong redox ability, (2) the large specific surface area, which provided abundant active sites and efficient adsorption performance and catalytic performance, and (3) the special morphology, which induced multiple reflections of light, thereby improving absorption and utilisation of light. Moreover, after four cycles of pyridine denitrification, the samples still exhibited high activity, indicating good stability and recyclability of the composite catalyst. These findings provide a basis for the development of composite PCs for efficient fuel denitration under visible light irradiation.
RESUMEN
Construction of step-scheme (S-scheme) heterojunction (HJ) structures is an excellent strategy to achieve efficient photogenerated carrier separation and retain strong redox ability. Recently, the development of efficient S-scheme HJ photocatalysts for the degradation of environmental organic pollutants has attracted considerable attention. In this work, a novel S-scheme CdS/Pt/Bi2MoO6 (CPB) photocatalyst was prepared for the first time by sonochemical and solvothermal methods. By anchoring Pt nanoparticles (NPs) at the interface between CdS nanorods (NRs) and Bi2MoO6 nanosheets (NSs), the migration of photogenerated electron-hole pairs along the stepped path was achieved. The ternary CPB samples were characterized by various analytical techniques, and their photocatalytic performance was investigated by conducting simulated fuel denitrification under visible-light irradiation. It was found that the CPB-4 composites exhibited the highest pyridine degradation activity, which reached 94% after 4 h of visible-light irradiation. The superior photocatalytic performance of the CPB-4 composite could be attributed to the synergistic effect of the Pt NPs and Bi2MoO6 NRs on the photocatalytic degradation as well as to the introduction of Pt and Bi2MoO6, which led to an excellent response and large specific surface area of the CPB-4 composite. Lastly, the bridging role of the Pt NPs introduced into the S-scheme system was also notable, as it effectively improved the separation and transfer of the CdS/Bi2MoO6 interfaces for the photogenerated electron-hole pairs while retaining strong redox ability.
RESUMEN
Creating two-dimensional (2D) crystal-metal heterostructures with an ultrathin thickness has spurred increasing research endeavors in catalysis because of its fascinating opportunities in tuning the electronic state at the surface and enhancing the chemical reactivity. Here we report a novel and facile Nb4+-assisted strategy for the in situ growth of highly dispersed Pd nanoparticles (NPs) on monolayer HNb3O8 nanosheets (HNb3O8 NS) constituting a 2D Pd/HNb3O8 NS heterostructure composite without using extra reducing agents and stabilizing agents. The Pd NP formation is directed via a redox reaction between an oxidative Pd salt precursor (H2PdCl4) and reductive unsaturated surface metal (Nb4+) sites induced by light irradiation on monolayer HNb3O8 NS. The periodic arrangement of metal Nb nodes on HNb3O8 NS leads to a homogeneous distribution of Pd NPs. Density functional theory (DFT) calculations reveal that the direct redox reaction between the Nb4+ and Pd2+ ions leads to a strong chemical interaction between the formed Pd metal NPs and the monolayer HNb3O8 support. Consequently, the as-obtained Pd/HNb3O8 composite serves as a highly efficient bifunctional catalyst in both heterogeneous thermocatalytic and photocatalytic selective reduction of aromatic nitro compounds in water under ambient conditions. The achieved high activity originates from the unique 2D nanosheet configuration and in situ Pd incorporation, which leads to a large active surface area, strong metal-support interaction and enhanced charge transport capability. Moreover, this facile Nb4+-assisted synthetic route has demonstrated to be general, which can be applied to load other metals such as Au and Pt on monolayer HNb3O8 NS. It is anticipated that this work can extend the facile preparation of noble metal/nanosheet 2D heterostructures, as well as promote the simultaneous capture of duple renewable thermal and photon energy sources to drive an energy efficient catalytic process.
RESUMEN
Applying Hirota's binary operator approach to the (2+1)-dimensional nonlinear Schrödinger equation with the radially variable diffraction and nonlinearity coefficients, we derive a variety of exact solutions to the equation. Based on the solitary wave solutions derived, we obtain some special soliton structures, such as the embedded, conical, circular, breathing, dromion, ring, and hyperbolic soliton excitations. For some specific choices of diffraction and nonlinearity coefficients, we discuss features of the (2+1)-dimensional multisolitonic solutions.
