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1.
Sci Bull (Beijing) ; 2024 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-39299873

RESUMO

The electrochemical oxidation of 5-hydroxymethylfurfural (HMFOR) in alkaline electrolyte is a promising strategy for producing high-value chemicals from biomass derivatives. However, the disproportionation of aldehyde groups under strong alkaline conditions and the polymerization of HMF to form humic substances can impact the purity of 2,5-furandicarboxylic acid (FDCA) products. The use of neutral electrolytes offers an alternative environment for electrolysis, but the lack of OH- ions in the electrolyte often leads to low current density and low yields of FDCA. In this study, a sandwich-structured catalyst, consisting of Ru clusters confined between unilamellar MnO2 nanosheets (S-Ru/MnO2), was used in conjunction with an electrochemical pulse method to realize the electrochemical conversion of 5-hydroxymethylfurfural into FDCA in neutral electrolytes. Pulse electrolysis and the strong electron transfer between Ru clusters and MnO2 nanosheets help maintain Ru in a low oxidation state, ensuring high activity. The increased *OH generation led to a groundbreaking current density of 47 mA/cm2 at 1.55 V vs. reversible hydrogen electrode (RHE) and an outstanding yield rate of 98.7 % for FDCA in a neutral electrolyte. This work provides a strategy that combines electrocatalyst design with an electrolysis technique to achieve remarkable performance in neutral HMFOR.

2.
Small ; : e2405106, 2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-39233535

RESUMO

Conventional herbicide formulations suffer from serious problems such as easy drift, run-off and scouring into the environment, which pose enormous threats to human health and environmental safety. Herein, an innovative strategy is proposed to prepare oil-in-water nanoemulsions with long-term stability, enhanced droplet deposition, and improved nanoherbicide adhesion via steerable interfacial assembly of 1D amyloid-like protein nanocomposites. Bovine serum albumin (BSA) undergoes rapid amyloid-like aggregation upon reduction of its disulfide bond. The resulting phase-transitioned BSA (PTB) oligomers instantly self-assemble on the surface of cellulose nanofibers (CNF) to form the 1D PTB/CNF nanocomposites, which greatly expands the parameter space for interfacial assembly of amyloid-like proteins. The PTB/CNF nanocomposites exhibit excellent interfacial activity, enabling spontaneous adsorption at the oil-water interface to stabilize nanoemulsion. The excess PTB/CNF nanocomposites would also self-assemble at the air-aqueous interface upon spraying, resulting in efficient droplet deposition on (super)hydrophobic leaves. The deposited nanoherbicides show excellent resistance to wind/rain corrosion due to the robust amyloid-mediated adhesion, with a retention rate of more than 80% after severe scouring. Consequently, herbicide applications can be reduced by at least 30% compared to commercial emulsifiable concentrates, showing greater herbicidal efficiency. This study provides novel insights and approaches to promote sustainable agricultural development.

3.
Small ; : e2404598, 2024 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-39291878

RESUMO

The endowment of metal organic frameworks (MOF) with superior electrocatalytic performance without compromising their structural/compositional superiorities is of great significance for the development of renewable energy devices, yet remains a grand challenge. Herein, a deliberate partial amorphization strategy is developed to construct a heterostructured electrocatalyst consisting of crystalline Co-MOF and amorphous Co-S nanoflake arrays aligned on the carbon cloth (CC) substrate (abbreviated as Co-MOF/Co-S@CC hereafter) through a rapid sulfuration method. The simultaneous implement of crystalline-amorphous (c-a) heterostructure and nanoflake arrayed architecture on CC substrate renders the Co-MOF/Co-S@CC with abundant and tight active sites, accelerated charge transfer rate, regulated electronic structures, and reinforced structural stability. As such, the obtained Co-MOF/Co-S@CC electrode demonstrates outstanding electrochemical hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances with the overpotentials of 64 and 217 mV at 10 mA cm-2, respectively. Moreover, a two-electrode electrolyzer assembled by Co-MOF/Co-S@CC electrodes exhibits the lower cell voltages and larger current densities than those of Pt/C and RuO2 counterparts, excellent reversibility and prominent long-term stability, representing a great prospect for feasible H2 production. This adopted concept of c-a heterostructure for electronic regulation may bring about insightful inspiration for designing high-performance electrocatalysts for sustainable energy systems.

4.
Molecules ; 29(17)2024 Sep 04.
Artigo em Inglês | MEDLINE | ID: mdl-39275034

RESUMO

Morphological control of metal-organic frameworks (MOFs) at the micro/nanoscopic scale is critical for optimizing the electrochemical properties of them and their derivatives. In this study, manganese organic phosphate (Mn-MOP) with three distinct two-dimensional (2D) morphologies was synthesized by varying the molar ratio of Mn2+ to phenyl phosphonic acid, and one of the morphologies is a unique palm leaf shape. In addition, a series of 2D Mn-MOP derivatives were obtained by calcination in air at different temperatures. Electrochemical studies showed that 2D Mn-MOP derivative calcined at 550 °C and exhibited a superior specific capacitance of 230.9 F g-1 at 0.5 A g-1 in 3 M KOH electrolyte. The aqueous asymmetric supercapacitor and the constructed flexible solid-state device demonstrated excellent rate performance. This performance reveals the promising application of 2D Mn-MOP materials for energy storage.

5.
Nanoscale ; 2024 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-39225065

RESUMO

The manipulation of rectifying contact between metal and semiconductor represents a powerful strategy to modify the electronic configuration of active sites for improved electrocatalytic performance. Herein, we present an NaCl template-assisted approach to rationally construct a Schottky electrocatalyst consisting of a honeycomb-like N-doped carbon matrix decorated with uniformly ultrasmall Ru nanoparticles with an average diameter of 2.5 nm (hereafter abbreviated as Ru NPs@HNC). It is found that the Fermi level difference between Ru and HNC can cause self-driven migration of electrons from Ru NPs to the HNC substrate, which leads to the generation of a built-in electric field and directional flow of electrons, thereby enhancing the intrinsic activity. In addition, the immobilization of ultrafine Ru NPs on the honeycomb-like carbon skeleton can effectively inhibit the undesired migration, agglomeration and detachment of the active sites, thus ensuring remarkable structural stability. As a result, the Ru NPs@HNC with optimal rectifying contact delivers superior electrochemical activity with a small overpotential of 28 mV at 10 mA cm-2 and outstanding long-term stability in an alkaline solution. The design philosophy of grain-size modulation and Schottky contact may widen up insight into the preparation of high-performance electrocatalysts in sustainable energy conversion systems.

6.
Nat Commun ; 15(1): 7150, 2024 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-39168967

RESUMO

Despite the prevalent of hexagonal, tetragonal, and triangular pore structures in two-dimensional covalent organic frameworks (2D COFs), the pentagonal pores remain conspicuously absent. We herein present the Cairo pentagonal tessellated COFs, achieved through precisely chosen geometry and metrics of the linkers, resulting in unprecedented mcm topology. In each pentagonal structure, porphyrin units create four uniform sides around 15.5 Å with 90° angles, while tetrabiphenyl unit establish a bottom edge about 11.6 Å with 120° angles, aligning precisely with the criteria of Cairo Pentagon. According to the narrow bandgap and strong near-infrared (NIR) absorbance, as-synthesized COFs exhibit the efficient singlet oxygen (1O2) generation and photothermal conversion, resulting in NIR photothermal combined photodynamic therapy to guide cancer cell apoptosis. Mechanistic studies reveal that the good 1O2 production capability upregulates intracellular lipid peroxidation, leading to glutathione depletion, low expression of glutathione peroxidase 4, and induction of ferroptosis. The implementation of pentagonal Cairo tessellations in this work provides a promising strategy for diversifying COFs with new topologies, along with multimodal NIR phototherapy.


Assuntos
Apoptose , Raios Infravermelhos , Fotoquimioterapia , Oxigênio Singlete , Humanos , Oxigênio Singlete/metabolismo , Oxigênio Singlete/química , Fotoquimioterapia/métodos , Estruturas Metalorgânicas/química , Porfirinas/química , Animais , Peroxidação de Lipídeos , Linhagem Celular Tumoral , Ferroptose , Fototerapia/métodos , Camundongos , Glutationa/química , Glutationa/metabolismo , Fármacos Fotossensibilizantes/química , Neoplasias/terapia , Neoplasias/metabolismo
7.
Nat Commun ; 15(1): 7356, 2024 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-39191759

RESUMO

The family of coinage-metal-based cyclic trinuclear complexes exhibits abundant photophysical properties, promising for diverse applications. However, their utility in biochemistry is often hindered by large particle size and strong hydrophobicity. Meanwhile, the investigation into multi-photon excited luminescence within this family remained undocumented, limiting their potential in bio-imaging. Herein, we unveil the multi-photon excited luminescent properties of pyrazolate-based trinuclear gold(I) clusters, facilitated by excimeric gold(I)···gold(I) interactions, revealing a nonlinear optical phenomenon within this family. Furthermore, to address issues of poor biocompatibility, we employ electrospinning coupled with hydroxypropyl-beta-cyclodextrin as the matrix to fabricate a flexible, durable, transparent, and red emissive film with a photoluminescence quantum yield as high as 88.3%. This strategy not only produces the film with sufficient hydrophilicity and stability, but also achieves the downsizing of trinuclear gold(I) clusters from microscale to nanoscale. Following the instantaneous dissolution of the film in the media, the released trinuclear gold(I) nanoparticles have illuminated cells and bacteria through a real-time, non-toxic, multi-photon bio-imaging approach. This achievement offers a fresh approach for utilizing coinage-metal-based cyclic trinuclear complexes in biochemical fields.


Assuntos
Ouro , Luminescência , Fótons , Ouro/química , Humanos , Nanopartículas Metálicas/química , Pirazóis/química , Células HeLa
8.
J Colloid Interface Sci ; 677(Pt B): 21-29, 2024 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-39133995

RESUMO

The architecture of electrodes plays a pivotal role in the transfer and transportation of charges during electrochemical reactions. Selecting optimal electrode materials and devising well-conceived electrode structures can substantially enhance the electrochemical performance of devices. This manuscript leverages 3D printing technology to fabricate asymmetric supercapacitor devices featuring regular layered configurations. By investigating the impact of various materials on the internal architecture of printed electrodes, we establish a stratified electrode structure with an orderly arrangement, thereby significantly improving asymmetric charge transfer between electrodes. The application of 3D printing technology to construct electrode structures effectively mitigates the agglomeration of electrode materials. The 3D-printed VCG//MXene devices demonstrate exceptional areal capacitance (205.57 mF cm-2) and energy density (60.03 µWh cm-2), with a power density of 0.174 W cm-2. Consequently, selecting appropriate materials for fabricating printable electrode structures and achieving efficient 3D printing is anticipated to offer novel insights into the construction and enhancement of miniature asymmetric micro-supercapacitor (MSCs) devices.

9.
Angew Chem Int Ed Engl ; : e202411579, 2024 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-39086196

RESUMO

Prussian blue analogues (PBAs) have been widely studied in aqueous zinc-ion batteries (AZIBs) due to the characteristics of large specific surface area, open aperture, and straightforward synthesis. In this work, vanadium-based PBA nanocubes were firstly prepared using a mild in-situ conversion strategy at room temperature without the protection of noble gas. Benefiting from the multiple-redox active sites of V3+/V4+, V4+/V5+ and Fe2+/Fe3+, the cathode exhibited an excellent discharge specific capacity of 200 mA h g-1 in AZIBs, which is much higher than those of other metal-based PBAs nanocubes. To further improve the long-term cycling stability of the V-PBA cathode, a high concentration water-in-salt electrolyte (4.5 M ZnSO4 + 3 M Zn(OTf)2), and a water-based eutectic electrolyte (5.55 M glucose + 3 M Zn(OTf)2) were designed to successfully inhibit the dissolution of vanadium and improve the deposition of Zn2+ onto the zinc anode. More importantly, the assembled AZIBs maintained 55% of their highest discharge specific capacity even after 10000 cycles at 10 A g-1 with superior rate capability. This study provides a new strategy for the preparation of pure PBA nanostructures and a new direction for enhancing the long-term cycling stability of PBA-based AZIBs at high current densities for industrialization prospects.

10.
Angew Chem Int Ed Engl ; : e202412890, 2024 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-39148428

RESUMO

The design of three-dimensional covalent organic frameworks (3D COFs) using linear and trigonal linkers remains challenging due to the difficulty in achieving a specific non-planar spatial arrangement with low-connectivity building units. Here, we report the novel 3D COFs with linear and trigonal linkers, termed TMB-COFs, exhibiting srs topology. The steric hindrance provides an additional force to alter the torsion angles of peripheral triangular units, guiding the linear unit to connect with the trigonal unit into 3D srs frameworks, rather than the more commonly observed two-dimensional (2D) hcb structures. Furthermore, we comprehensively examined the hydrogen peroxide photocatalytic production capacity of the TMB-COFs in comparison with analogous 2D COFs. The experimental results and DFT calculations demonstrate a significant enhancement in photocatalytic hydrogen peroxide production efficacy through framework regulation. This work emphasizes the steric configuration using low connectivity building units, offering a fresh perspective on the design and application of 3D COFs.

11.
Adv Sci (Weinh) ; : e2403802, 2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39140249

RESUMO

Exploring new carbon-based electrode materials is quite necessary for enhancing capacitive deionization (CDI). Here, hollow mesoporous carbon spheres (HMCSs)/metal-organic frameworks (MOFs) derived carbon materials (NC(M)/HMCSs and NC(M)@HMCSs) are successfully prepared by interface-coating and space-encapsulating design, respectively. The obtained NC(M)/HMCSs and NC(M)@HMCSs possess a hierarchical hollow nanoarchitecture with abundant nitrogen doping, high specific surface area, and abundant meso-/microporous pores. These merits are conducive to rapid ion diffusion and charge transfer during the adsorption process. Compared to NC(M)/HMCSs, NC(M)@HMCSs exhibit superior electrochemical performance due to their better utilization of the internal space of hollow carbon, forming an interconnected 3D framework. In addition, the introduction of Ni ions is more conducive to the synergistic effect between ZIF(M)-derived carbon and N-doped carbon shell compared with other ions (Mn, Co, Cu ions). The resultant Ni-1-800-based CDI device exhibits excellent salt adsorption capacity (SAC, 37.82 mg g-1) and good recyclability. This will provide a new direction for the MOF nanoparticle-driven assembly strategy and the application of hierarchical hollow carbon nanoarchitecture to CDI.

12.
Adv Mater ; : e2408396, 2024 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-39101297

RESUMO

The rechargeable aqueous ammonium ion battery shows great potential in low-cost energy storage system because of its long life and environmental friendliness. However, most inorganic host materials used in ammonium ion batteries are still limited by slow diffusion kinetics. Herein, it is identified that a 2D heteroligand-based copper-organic framework featuring numerous ammonium ion adsorption site in the π-conjugated periodic skeleton supplies multiple accessible redox-active sites for high-performance ammonium storage. Benefitting from the effective regulation of electron delocalization by heteroligand and the inherent hydrogen bond cage mechanism between ammonium ions, the resultant full battery delivers a large specific energy density of 211.84 Wh kg-1, and it can be stably operated for 12000 cycles at 5 A g-1 for over 80 days. This explanatory understanding provides a new idea for the rational design of high-performance MOF-based ammonium ion battery cathode materials for efficient energy storage and conversion in the future.

13.
Angew Chem Int Ed Engl ; : e202414650, 2024 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-39206502

RESUMO

Investigating the formation and transformation mechanisms of spiral-concave crystals holds significant potential for advancing innovative material design and comprehension. We examined the kinetics-controlled nucleation and growth mechanisms of Prussian Blue crystals with spiral concave structures, and constructed a detailed crystal growth phase diagram. The spiral-concave hexacyanoferrate (SC-HCF) crystals, characterized by high-density surface steps and a low stress-strain architecture, exhibit enhanced activity due to their facile interaction with reactants. Notably, the coordination environment of SC-HCF can be precisely modulated by the introduction of diverse metals. Utilizing X-ray absorption fine structure spectroscopy and in-situ ultraviolet-visible spectroscopy, we elucidated the formation mechanism of SC-HCF to Co-HCF facilitated by oriented adsorption-ion exchange (OA-IE) process. Both experimental data, and density functional theory confirm that Co-HCF possesses an optimized energy band structure, capable of adjusting the local electronic environment and enhancing the performance of the oxygen evolution reaction. This work not only elucidates the formation mechanism and coordination regulation for rich steps HCF, but also offers a novel perspective for constructing nanocrystals with intricate spiral-concave structures.

14.
Angew Chem Int Ed Engl ; : e202409838, 2024 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-39058295

RESUMO

Rechargeable aqueous zinc-ion (Zn-ion) batteries are widely regarded as important candidates for next-generation energy storage systems for low-cost renewable energy storage. However, the development of Zn-ion batteries is currently facing significant challenges due to uncontrollable Zn dendrite growth and severe parasitic reactions on Zn metal anodes. Herein, we report an innovative strategy to improve the performance of aqueous Zn-ion batteries by leveraging the self-assembly of bovine serum albumin (BSA) into a bilayer configuration on Zn metal anodes. BSA's hydrophilic and hydrophobic fragments form unique and intelligent ion channels, which regulate the migration of Zn ions and facilitate their desolvation process, significantly diminishing parasitic reactions on Zn anodes and leading to a uniform Zn deposition along the Zn (002) plane. Notably, the Zn||Zn symmetric cell with BSA as the electrolyte additive demonstrated a stable cycling performance for up to 2400 hours at a high current density of 10 mA cm-2. This work demonstrates the pivotal role of self-assembled protein bilayer structures in improving the durability of Zn anodes in aqueous Zn-ion batteries.

15.
Inorg Chem ; 63(28): 13093-13099, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-38953699

RESUMO

Designing and synthesizing hollow frame structures with unique three-dimensional open structures in electrocatalysis remain a challenge. Etching is an effective method to synthesize metal-organic frameworks (MOFs) with a hollow structure and rich function. Herein, we report the design and synthesis of Hf-doped CoP hollow nanocubes by selective etching and ion exchange. Different from the traditional etching method, we used acid xylenol orange solution to etch typically the (211) crystal face of ZIF-67, obtaining the unique bell-like structure, named XO-ZIF-67. Subsequently, Hf-doped CoP hollow nanocubes were formed by Hf4+ doping and simple phosphating treatment. Electrochemical tests showed that the overpotential of the obtained catalyst is only 291 mV at the current density of 10 mA cm-2 when applied in catalyzing the oxygen evolution reaction (OER). Furthermore, the catalyst shows excellent stability when running in 1 M KOH solution for 25 h.

16.
Adv Mater ; : e2408317, 2024 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-39081106

RESUMO

Aqueous zinc-iodine batteries (AZIBs) are highly appealing for energy requirements owing to their safety, cost-effectiveness, and scalability. However, the inadequate redox kinetics and severe shuttling effect of polyiodide ions impede their commercial viability. Herein, several Zn-MOF-derived porous carbon materials are designed, and the further preparation of iron-doped porous carbon (Fe-N-C, M9) with varied Fe doping contents is optimized based on a facile self-assembly/carbonization approach. M9, with atomic Fe coordinated to nitrogen atoms, is employed as an efficient cathode host for AZIBs. Functional modifications of porous carbon hosts involving the doping species and levels are investigated. The adsorption tests, in situ Raman spectroscopy, and in situ UV-vis results demonstrate the adsorption capability and charge-discharge mechanism for the iodine species. Furthermore, experimental findings and theoretical analyses have proven that the redox conversion of iodine is enhanced through a physicochemical confinement effect. This study offers basic principles for the strategic design of single-atom dispersed carbon as an iodine host for high-performance AZIBs. Flexible soft-pack battery and wearable microbattery applications also have implications for future long-life aqueous battery designs.

17.
ACS Appl Mater Interfaces ; 16(32): 42352-42362, 2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39080825

RESUMO

To enhance the efficiency of oxygen reduction reaction (ORR) catalysts, precise control over the adsorption/desorption energy barriers of oxygen intermediates at atomically dispersed Fe-N-C sites is essential yet challenging. Addressing this, we employed a pyrolysis approach using a nitrogen-containing polymer to fabricate Fe single-atom (SA) catalysts embedded in a pyridinic-N enriched carbon matrix. This synthesis strategy yielded Fe SAs that demonstrated a superior electrochemical ORR performance, evidenced by an impressive half-wave potential of 0.941 V and a high limiting current density of 5.72 mA/cm2. Moreover, when applied in homemade Zn-air batteries, this premier catalyst exhibited exceptional specific capacity (720 mAh/gZn), peak power density (253 mW/cm2), and notable long-term stability. Theoretical insights revealed that the increased pyridinic-N content in the catalyst facilitated efficient electron transfer from N atoms to the Fe active sites, thus fine-tuning the d-band center and effectively controlling the adsorption energy barrier of *OH species. These mechanisms synergistically improve the ORR performance. Crucially, this fabrication method shows promise for adaptation to other transition metal-based SAs, including Co, Ni, and Cu, potentially establishing a versatile synthesis route for developing atomically dispersed catalyst systems in future applications.

18.
ACS Omega ; 9(28): 30571-30582, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-39035970

RESUMO

Ulcerative colitis (UC) is a chronic inflammatory bowel disease characterized by the disruption of the intestinal epithelial barrier. This study described the synthesis and characterization of CCM-Co-ZIF-8, a novel composite material with enzyme-like activities similar to catalase, peroxidase, and superoxide dismutase. CCM-Co-ZIF-8 demonstrated the ability to scavenge reactive oxygen species that play a critical role in UC pathogenesis. In vitro studies using lipopolysaccharide-induced RAW264.7 cells showed that CCM-Co-ZIF-8 exhibited anti-inflammatory activity by promoting the transition of macrophages from an M1 to an M2 phenotype. In vivo experiments using a mouse model of UC demonstrated that CCM-Co-ZIF-8 suppressed the expression of proinflammatory cytokines. These findings suggested that CCM-Co-ZIF-8 might hold promise as a therapeutic strategy for the treatment of UC.

19.
Angew Chem Int Ed Engl ; 63(36): e202410255, 2024 Sep 02.
Artigo em Inglês | MEDLINE | ID: mdl-38881320

RESUMO

Metal-organic frameworks (MOFs) are considered as a promising candidate for advancing energy storage owing to their intrinsic multi-channel architecture, high theoretical capacity, and precise adjustability. However, the low conductivity and poor structural stability lead to unsatisfactory rate and cycling performance, greatly hindering their practical application. Herein, we propose a sea urchin-like Co-ZIF-L superstructure using molecular template to induce self-assembly followed by ion exchange method, which shows improved conductivity, successive channels, and high stability. The ion exchange can gradually etch the superstructure, leading to the reconstruction of Co-ZIF-L with three-dimensional (3D) cross-linked ultrathin porous nanosheets. Moreover, the precise control of Co to Ni ratios can construct effective micro-electric field and synergistically enhance the rapid transfer of electrons and electrolyte ions, improving the conductivity and stability of CoNi-ZIF-L. The Co6.53Ni-ZIF-L electrode exhibits a high specific capacity (602 F g-1 at 1 A g-1) and long cycling stability (95.3 % retention after 4,000 cycles at 5 A g-1). The Co6.53Ni-ZIF-L//AC asymmetric flexible supercapacitor employing gel electrolyte also exhibits excellent cycling stability (93.3 % retention after 4000 cycles at 5 A g-1). This discovery provides valuable insights for electrode material selection and energy storage efficiency improvement.

20.
Angew Chem Int Ed Engl ; 63(35): e202408989, 2024 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-38837505

RESUMO

The extensive industrial applications of fuel oil, a critical strategic resource, are accompanied by significant environmental and health concerns due to the presence of sulfur-containing compounds in its composition, which result in hazardous combustion waste. Extensive research has been conducted to develop technologies for low-vulcanization fuel production to address this issue. Consequently, the investigation of catalysts for environmentally friendly and safe photocatalytic desulfurization becomes imperative. To that end, we have designed efficient MIL-101(Fe)/CQDs@g-C3N4 (MIL101/CDs-C3N4) Z-scheme heterojunction photocatalysts with high carrier separation and mobility through a thermal polymerization-hydrothermal strategy. The high concentration of photogenerated carriers facilitates the activation of oxygen and H2O2, leading to increased production of ROS (⋅O2 -, ⋅OH, h+), thereby enhancing the photocatalytic desulfurization (PODS). Additionally, DFT (Density functional theory) calculations were utilized to determine the electron migration pathways of the catalysts and adsorption energies of DBT (dibenzothiophene). Moreover, Gibbs free energy calculations indicated that MIL101/CDs-C3N4 exhibited the lowest activation energy for oxygen and H2O2. The mechanism of photocatalytic desulfurization was proposed through a combination of theoretical calculations and experimental studies. This study provides guidance for the development of MOF-based Z-scheme systems and their practical application in desulfurization processes.

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