ABSTRACT
Artificial photosynthesis is a promising approach to produce clean fuels via renewable solar energy. However, it is practically constrained by two issues of slow photogenerated carrier migration and rapid electron/hole recombination. It is also a challenge to achieve a 2:1 ratio of H2 and O2 for overall water splitting. Here we report a rational design of spatially differentiated two-dimensional Bi4Ti3O12 nanosheets to enhance overall water splitting. Such a spatially differentiated structure overcomes the limitation of charge transfer across different crystal planes in a single crystal semiconductor. The experimental results show a redistribution of charge within a crystal plane. The resulting photocatalyst produces 40.3 µmol h-1 of hydrogen and 20.1 µmol h-1 of oxygen at a near stoichiometric ratio of 2:1 and a solar-to-hydrogen efficiency of 0.1% under simulated solar light.
ABSTRACT
Metal phosphide, as a highly conductive, chemically stable catalyst material, modulating its hydrogen adsorption is crucial to enhance hydrogen evolution reaction (HER) activity. In this study, we propose a double loading strategy to build Ag and AgP2 heterogeneous structures on Ni2P nanosheets (Ag-AgP2/Ni2P). This is the first application of AgP2 materials in HER. This innovative synthesis was achieved by liquid-phase adsorption of precursors and heat-treatment phosphorization, surface adsorbed AgNO3 is converted to Ag-AgP2 double loading at the same time as Ni2P formation. Density functional theory (DFT) calculations reveal that the double loading structure optimizes charge distribution and d-band center. Its hydrogen adsorption free energy is closer to electroneutrality than that of single loading and simple heterostructures. Benefiting from the special structure, Ag-AgP2/Ni2P exhibits excellent HER performance in alkaline media, requiring only 78 mV overpotential to reach 10 mA cm-2 and stability up to 200 h. This dual loading strategy broadens the perspective of heterogeneous electrocatalyst development.
ABSTRACT
Efficient production of green hydrogen energy is crucial in addressing the energy crisis and environmental concerns. The oxygen evolution reaction (OER) poses a challenge in conventional overall water electrolysis due to its slow thermodynamically process. Urea oxidation reaction (UOR) offers an alternative anodic oxidation method that is highly efficient and cost-effective, with favorable thermodynamics and sustainability. Recently, there has been limited research on bifunctional catalysts that exhibit excellent activity for both OER and UOR reactions. In this study, we developed a selenium and iron co-doped nickel sulfide (SeFe-Ni3S2) catalyst that demonstrated excellent Tafel slopes of 53.9 mV dec-1 and 16.4 mV dec-1 for OER and UOR, respectively. Density Functional Theory (DFT) calculations revealed that the introduction of metal (iron) and nonmetallic elements (selenium) was found to coordinate the d-band center, resulting in improved adsorption/desorption energies of the catalysts and reduced the overpotentials and limiting potentials for OER and UOR, respectively. This activity enhancement can be attributed to the altered electronic coordination structure after the introduction of selenium (Se) and iron (Fe), leading to an increase in the intrinsic activity of the catalyst. This work offers a new strategy for bifunctional catalysts for OER and UOR, presenting new possibilities for the future development of hydrogen production and novel energy conversion technologies. It contributes towards the urgent search for technologies that efficiently produce green hydrogen energy, providing potential solutions to mitigate the energy crisis and protect the environment.
ABSTRACT
Transition metal-based oxyhydroxides (MOOH) have garnered significant attention as promising catalyst for the Oxygen Evolution Reaction (OER). However, the direct synthesis of MOOH poses challenges due to the instability of trivalent cobalt and nickel salts, attrivuted to their high oxidation states. In this study, theoretical computations predicted that Co(OH)2 nanosheets are exclusively formed on carbon structures, owing to the stronger binding energy between CoOOH and CC compared to Co(OH)2. Furthermore, the presence of FeOOH interface reduces the binding energy between CoOOH and carbon structure. Experiment evidence confirms that CoOOH can be directly synthesized through controlled epitaxial growth on an FeOOH interface using a hydrothermal method. Moreover, the in-situ doping of iron leads to the formation of high-quality Fe0.35Co0.65OOH with exceptional OER performance, displaying a low overpotential of 240 mV at 10 mA cm-2 and a small Tafel slope of 43 mV dec-1. Density functional theory (DFT) calculations uncover the substantial enhancement of oxygen-containing species adsorption abilities by Fe0.35Co0.65OOH, resulting in improved OER activity. This work presents a promising strategy for the efficient preparation of layered cobalt oxyhydroxides, enabling efficient energy conversion and storage.
ABSTRACT
Nanozymes have demonstrated significant potential in combating malignant tumor proliferation through catalytic therapy. However, the therapeutic effect is often limited by insufficient catalytic performance. In this study, we propose the utilization of strain engineering in metallenes to fully expose the active regions due to their ultrathin nature. Here, we present the first report on a novel tensile strain-mediated local amorphous RhRu (la-RhRu) bimetallene with exceptional intrinsic photothermal effect and photo-enhanced multiple enzyme-like activities. Through geometric phase analysis, electron diffraction profile, and X-ray diffraction, it is revealed that crystalline-amorphous heterophase boundaries can generate approximately 2 % tensile strain in the bimetallene. The ultrathin structure and in-plane strain of the bimetallene induce an amplified strain effect. Both experimental and theoretical evidence support the notion that tensile strain promotes multiple enzyme-like activities. Functioning as a tumor microenvironment (TME)-responsive nanozyme, la-RhRu exhibits remarkable therapeutic efficacy both in vitro and in vivo. This work highlights the tremendous potential of atomic-scale tensile strain engineering strategy in enhancing tumor catalytic therapy.
Subject(s)
Photothermal Therapy , Humans , Catalysis , Animals , Mice , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Neoplasms/drug therapy , Neoplasms/therapy , Tensile Strength , Cell Line, Tumor , Tumor Microenvironment/drug effectsABSTRACT
The precise design of single-atom nanozymes (SAzymes) and understanding of their biocatalytic mechanisms hold great promise for developing ideal bio-enzyme substitutes. While considerable efforts have been directed towards mimicking partial bio-inspired structures, the integration of heterogeneous SAzymes configurations and homogeneous enzyme-like mechanism remains an enormous challenge. Here, we show a spatial engineering strategy to fabricate dual-sites SAzymes with atomic Fe active center and adjacent Cu sites. Compared to planar Fe-Cu dual-atomic sites, vertically stacked Fe-Cu geometry in FePc@2D-Cu-N-C possesses highly optimized scaffolds, favorable substrate affinity, and fast electron transfer. These characteristics of FePc@2D-Cu-N-C SAzyme induces biomimetic O2 activation through homogenous enzymatic pathway, resembling functional and mechanistic similarity to natural cytochrome c oxidase. Furthermore, it presents an appealing alternative of cytochrome P450 3A4 for drug metabolism and drug-drug interaction. These findings are expected to deepen the fundamental understanding of atomic-level design in next-generation bio-inspired nanozymes.
Subject(s)
Biomimetics , Electron Transport Complex IV , Biocatalysis , Electron Transport , Engineering , CatalysisABSTRACT
Biochar is a promising sorbent for Cd removal from water, while the disposal of the exhausted Cd-enriched biochar remains a challenge. In this study, pyrolysis was employed to treat the exhausted biochar under N2 and CO2 atmospheres at 600-900 °C, and the fate of Cd during pyrolysis and characteristics of high-valued products were determined. The results indicated that higher temperature and CO2 atmosphere favored the volatilization of Cd. Based on the toxicity characteristic leaching procedure (TCLP) results, the pyrolysis treatment under both atmospheres enhanced the stability of Cd, and the leached Cd concentration of regenerated biochar obtained at high temperatures (>800 °C) was lower than 1 mg/L. Compared with the pristine biochar, the regenerated biochar demonstrated higher carbon content and pH, whereas the contents of oxygen and hydrogen declined, and exhibited promising sorption properties (35.79 mg/g). The atmosphere played an important role in modifying biochar properties and syngas composition. The N2 atmosphere facilitated CH4 production, whereas the CO2 atmosphere increased the proportion of CO. These results implied that pyrolysis can be a valuable and environmental-friendly strategy for the treatment and reuse of exhausted biochar sorbent.
Subject(s)
Cadmium , Pyrolysis , Carbon Dioxide , Charcoal/chemistryABSTRACT
Metal single-atom catalysts represent one of the most promising non-noble metal catalysts for the oxygen reduction reaction (ORR). However, they still suffer from insufficient activity and, particularly, durability for practical applications. Leveraging density functional theory (DFT) and machine learning (ML), we unravel an unexpected collective effect between FeN4OH sites, CeN4OH motifs, Fe nanoparticles (NPs), and Fe-CeO2 NPs. The collective effect comprises differently-weighted electronic and geometric interactions, whitch results in significantly enhanced ORR activity for FeN4OH active sites with a half-wave potential (E1/2) of 0.948â V versus the reversible hydrogen electrode (VRHE) in alkaline, relative to a commercial Pt/C (E1/2, 0.851â VRHE). Meanwhile, this collective effect endows the shortened Fe-N bonds and the remarkable durability with negligible activity loss after 50,000â potential cycles. The ML was used to understand the intricate geometric and electronic interactions in collective effect and reveal the intrinsic descriptors to account for the enhanced ORR performance. The universality of collective effect was demonstrated effective for the Co, Ni, Cu, Cr, and Mn-based multicomponent ensembles. These results confirm the importance of collective effect to simultaneously improve catalytic activity and durability.
ABSTRACT
Metallene materials can provide a large number of active catalytic sites for the efficient use of noble metals as catalysts for hydrogen evolution reaction (HER), whereas the intrinsic activity on the surface is insufficient in crystal phase. The amorphous phase with an inherent long-range disorder can offer a rich coordinate environment and charge polarization on the surface is proposed for promoting the intrinsic catalytic activity on the surface of noble metals. Herein, we designed an amorphous RuPd (am-RuPd) structure by the first principles molecular dynamics method. The performance of the acidic HER on am-RuPd can have a huge enhancement due to the free energy change of hydrogen adsorption close to zero. In alkaline conditions, the H2O dissociation energy barrier on am-RuPd is just 0.49 eV, and it is predicted that the alkaline HER performance of am-RuPd will largely exceed that of Pt nanocrystalline sheets. This work provides a strategy for enhancing the intrinsic catalytic activity on the surface and a way to design an efficient HER catalyst based on metallene materials used in both acidic and alkaline conditions.
ABSTRACT
MXenes are a class of 2D materials that include layered transition metal carbides, nitrides, and carbonitrides. Since their inception in 2011, they have garnered significant attention due to their diverse compositions, unique structures, and extraordinary properties, such as high specific surface areas and excellent electrical conductivity. This versatility has opened up immense potential in various fields, catalyzing a surge in MXene research and leading to note worthy advancements. This review offers an in-depth overview of the evolution of MXenes over the past 5 years, with an emphasis on synthetic strategies, structure-property relationships, and technological prospects. A classification scheme for MXene structures based on entropy is presented and an updated summary of the elemental constituents of the MXene family is provided, as documented in recent literature. Delving into the microscopic structure and synthesis routes, the intricate structure-property relationships are explored at the nano/micro level that dictate the macroscopic applications of MXenes. Through an extensive review of the latest representative works, the utilization of MXenes in energy, environmental, electronic, and biomedical fields is showcased, offering a glimpse into the current technological bottlenecks, such asstability, scalability, and device integration. Moreover, potential pathways for advancing MXenes toward next-generation technologies are highlighted.
ABSTRACT
Although S-scheme artificial photosynthesis shows promise for photocatalytic hydrogen production, traditional methods often overly concentrate on a single reduction site. This limitation results in inadequate redox capability and inefficient charge separation, which hampers the efficiency of the photocatalytic hydrogen evolution reaction. To overcome this limitation, a double S-scheme system is proposed that leverages dual reduction sites, thereby preserving energetic photo-electrons and holes to enhance apparent quantum efficiency. The design features a double S-scheme junction consisting of CdS nanospheres decorated with anatase TiO2 nanoparticles coupled with graphitic C3 N4 . The as-prepared catalyst exhibits a hydrogen evolution rate of 26.84 mmol g-1 h-1 and an apparent quantum efficiency of 40.2% at 365 nm. This enhanced photocatalytic hydrogen evolution is ascribed to the efficient charge separation and transport induced by the double S-scheme. Both theoretical calculations and comprehensive spectroscopy tests (both in situ and ex situ) affirm the efficient charge transport across the catalyst interface. Moreover, substituting the reduction-type catalyst CdS with other similar sulfides like ZnIn2 S4 , ZnS, MoS2 and In2 S3 further confirms the feasibility of the proposed double S-scheme configuration. The findings provide a pathway to designing more effective double S-scheme artificial photosynthetic systems, opening up fresh perspectives in enhancing photocatalytic hydrogen evolution performance.
ABSTRACT
Achieving a balance between H-atom adsorption and binding with H2 desorption is crucial for catalyzing hydrogen evolution reaction (HER). In this study, the feasibility of designing and implementing built-in opposite electric fields (OEF) is demonstrated to enable optimal H atom adsorption and H2 desorption using the Ni3(BO3)2/Ni5P4 heterostructure as an example. Through density functional theory calculations of planar averaged potentials, it shows that opposite combinations of inward and outward electric fields can be achieved at the interface of Ni3(BO3)2/Ni5P4, leading to the optimization of the H adsorption free energy (ΔGH*) near electric neutrality (0.05 eV). Based on this OEF concept, the study experimentally validated the Ni3(BO3)2/Ni5P4 system electrochemically forming Ni3(BO3)2 through cyclic voltammetry scanning of B-doped Ni5P4. The surface of Ni3(BO3)2 undergoes reconstruction, as characterized by Grazing Incidence Wide-Angle X-ray Scattering (GIWAXS) and in situ Raman spectroscopy. The resulting catalyst exhibits excellent HER activity in alkaline media, with a low overpotential of 33 mV at 10 mA cm-2 and stability maintained for over 360 h. Therefore, the design strategy of build-in opposite electric field enables the development of high-performance HER catalysts and presents a promising approach for electrocatalyst advancement.
ABSTRACT
Addressing the limitations arising from the consistent catalytic behavior observed for various intermediates during the electrochemical carbon dioxide reduction reaction (CO2 RR) poses a significant challenge in the optimization of catalytic activity. In this study, we aimed to address this challenge by constructing an asymmetric coordination Fe single atom catalyst (SCA) with a dynamically evolved structure. Our catalyst, consisting of a Fe atom coordinated with one S atom and three N atoms (Fe-S1 N3 ), exhibited exceptional selectivity (CO Faradaic efficiency of 99.02 %) and demonstrated a high intrinsic activity (TOF of 7804.34â h-1 ), and remarkable stability. Using operando XAFS spectra and Density Functional Theory (DFT) calculations, we elucidated the self-relaxation of geometric distortion and dynamic evolution of bond lengths within the catalyst. These structure changes enabled independent regulation of the *COOH and *CO intermediate adsorption energies, effectively breaking the linear scale relationship and enhancing the intrinsic activity of CO2 RR. This study provides valuable insights into the dynamic evolution of SACs and paves the way for targeted catalyst designs aimed to disrupt the linear scaling relationships.
ABSTRACT
Electrochemical carbon dioxide reduction reaction (CO2RR) involves a variety of intermediates with highly correlated reaction and ad-desorption energies, hindering optimization of the catalytic activity. For example, increasing the binding of the *COOH to the active site will generally increase the *CO desorption energy. Breaking this relationship may be expected to dramatically improve the intrinsic activity of CO2RR, but remains an unsolved challenge. Herein, we addressed this conundrum by constructing a unique atomic dispersed hetero-pair consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier. This system shows an unprecedented CO2RR intrinsic activity with TOF of 3336 h-1, high selectivity toward CO production, Faradaic efficiency of 95.96% at - 0.60 V and excellent stability. Theoretical calculations show that the Mo-Fe diatomic sites increased the *COOH intermediate adsorption energy by bridging adsorption of *COOH intermediates. At the same time, d-d orbital coupling in the Mo-Fe di-atom results in electron delocalization and facilitates desorption of *CO intermediates. Thus, the undesirable correlation between these steps is broken. This work provides a promising approach, specifically the use of di-atoms, for breaking unfavorable relationships based on understanding of the catalytic mechanisms at the atomic scale.
ABSTRACT
The effective design and construction of high-performance methanol oxidation reaction (MOR) electrocatalysts are significant for the development of direct methanol fuel cells. But the active sites of the MOR electrocatalysts are susceptible to being poisoned by CO, resulting in poor durability. Herein, we report an atomically dispersed CrOX species anchored on Pd metallene through bridging O atoms. This catalyst shows an outstanding MOR performance with 7 times higher mass activity and 100 mV lower CO electrooxidation potential than commercial Pd/C. The results of operando electrochemical Fourier transform infrared spectroscopy demonstrate the rapid removal of CO* on CrOX-Pd metallene. Theoretical calculations reveal that atomically dispersed CrOX can lower the adsorption energy of CO* on Pd sites and enhance that of OH* through the formation of a hydrogen bond, decreasing the formation energy of COOH*. This work provides a new strategy for improving MOR performance via atomically engineering oxide/metal interfaces.
ABSTRACT
Titanium dioxide (TiO2 ) stands out as a versatile transition-metal oxide with applications ranging from energy conversion/storage and environmental remediation to sensors and optoelectronics. While extensively researched for these emerging applications, TiO2 has also achieved commercial success in various fields including paints, inks, pharmaceuticals, food additives, and advanced medicine. Thanks to the tunability of their structural, morphological, optical, and electronic characteristics, TiO2 nanomaterials are among the most researched engineering materials. Besides these inherent advantages, the low cost, low toxicity, and biocompatibility of TiO2 nanomaterials position them as a sustainable choice of functional materials for energy conversion. Although TiO2 is a classical photocatalyst well-known for its structural stability and high surface activity, TiO2 -based photocatalysis is still an active area of research particularly in the context of catalyzing artificial photosynthesis. This review provides a comprehensive overview of the latest developments and emerging trends in TiO2 heterostructures and hybrids for artificial photosynthesis. It begins by discussing the common synthesis methods for TiO2 nanomaterials, including hydrothermal synthesis and sol-gel synthesis. It then delves into TiO2 nanomaterials and their photocatalytic mechanisms, highlighting the key advancements that have been made in recent years. The strategies to enhance the photocatalytic efficiency of TiO2 , including surface modification, doping modulation, heterojunction construction, and synergy of composite materials, with a specific emphasis on their applications in artificial photosynthesis, are discussed. TiO2 -based heterostructures and hybrids present exciting opportunities for catalyzing solar fuel production, organic degradation, and CO2 reduction via artificial photosynthesis. This review offers an overview of the latest trends and advancements, while also highlighting the ongoing challenges and prospects for future developments in this classical yet rapidly evolving field.
ABSTRACT
Asparagus officinalis is a health-care vegetable with homology value of medicine and food. The quality of A. officinalis is greatly different from various cultivars. It is essential to reveal the relationship between the variety and quality. This study investigated six nutritional compositions in ten A. officinalis cultivars, including amino acid, mineral substance, carbohydrate, vitamin C, protein and total sugar. Five chemometrics methods were further employed to evaluate their quality. The results consistently showed that ten varieties were divided into three grades as nutritional composition differences. HuaMiaoF1, JinGuan and FeiCuiMingZhu were grouped into cluster3 with the best quality, and Atlas and Jersey Giant were grouped into cluster1 with the lowest quality. Therefore, HuaMiaoF1, JinGuan and FeiCuiMingZhu can be suggested as good raw materials for medicine, food and health-care products industries. Meanwhile, the comprehensive application of five chemometrics methods was confirmed as a reliable methodology for quality evaluation of A. officinalis.
Subject(s)
Asparagus Plant , Asparagus Plant/chemistry , Functional Food , Ascorbic AcidABSTRACT
Photocatalytic water splitting holds great promise as a sustainable and cost-effectiveness alternative for the production of hydrogen. Nevertheless, the practical implementation of this strategy is hindered by suboptimal visible light utilization and sluggish charge carrier dynamics, leading to low yield. MXene is a promising cocatalyst due to its high conductivity, abundance of active sites, tunable terminal functional groups, and great specific surface area. Homo-interface has perfect lattice matching and uniform composition, which are more conducive to photogenerated carriers' separation and migration. In this study, a novel ternary heterogeneous photocatalyst, a-TiO2 /H-TiO2 /Ti3 C2 MXene (MXTi), is presented using an electrostatic self-assembly method. Compared to commercial P25, pristine anatase, and rutile TiO2 , as-prepared MXTi exhibit exceptional photocatalytic hydrogen evolution performance, achieving a rate of 0.387 mmol h-1 . The significant improvement is attributable to the synergistic effect of homo-interface engineering and Ti3 C2 MXene, which leads to widened light absorption and efficient carrier transportation. The findings highlight the potential of interface engineering and MXene cocatalyst loading as a proactive approach to enhance the performance of photocatalytic water splitting, paving the way for more sustainable and efficient hydrogen production.
ABSTRACT
Magnetic biochar is excellent for separation and peroxymonosulfate (PMS) activation. Copper doping could improve the catalytic capability of magnetic biochar significantly. In this study, cow dung biochar is applied to investigate the effects of copper doping on the magnetic biochar, focusing on the specific influence on the consumption of active sites, the production of oxidative species and the toxicity of degradation intermediates. The results showed that copper doping promoted the uniform distribution of iron sites on the biochar surface and reduced iron aggregation. At the same time, copper doping interpreted the biochar with larger specific surface area, which was beneficial to the adsorption and degradation of sulfamethoxazole (SMX). The SMX degradation kinetic constant with copper-doped magnetic biochar was 0.0403 min-1, which was 1.45 times than that of magnetic biochar. Besides, copper doping might accelerate the consumption of CO, Fe0, Fe2+ sites and hinder the activation of PMS at copper-related sites. Furthermore, copper doping promoted the PMS activation by magnetic biochar through accelerated electron transfer. For the oxidative species, copper doping accelerated the production of hydroxyl radicals, singlet oxygen, and superoxide radicals in solution and inhibited the generation of sulfate radicals. In addition, SMX could be directly decomposed into less toxic intermediates in the copper-doped magnetic biochar/PMS system. In conclusion, this paper provides insight and analysis of the advantages of copper doping on the magnetic biochar, which helps to facilitate the design and practical application of bimetallic biochar.
Subject(s)
Sulfamethoxazole , Water Pollutants, Chemical , Sulfamethoxazole/chemistry , Copper , Water Pollutants, Chemical/chemistry , Peroxides/chemistry , Iron/chemistry , Magnetic PhenomenaABSTRACT
Co-exposure of tetracycline (TC) and polyethylene microplastic (MP-PE) pollution might result in more intricate effects on rice growth and grain quality. In present study, two different rice cultivars of contrasting drought tolerance, Hanyou73 (H73, drought-resistant) and Quanyou280 (Q280, drought-sensitive) were grown on MP-PE and TC-contaminated soils under drought. It was found that drought stress had different influence on TC accumulation in the two rice cultivars. H73 accumulated more TC in leaves and grains without drought stress while Q280 accumulated more TC under drought stress. Furthermore, metabolomics results demonstrated that under drought stress, about 80 % of metabolites in H73 and 95 % in Q280 were down-regulated as compared to non-drought treatments. These findings provide insights into the effects of TC and MP-PE with and without drought stress on potential risks to rice growth and grain quality, which has implications on rice production and cultivar election under multiple-stress conditions.