Diffusion Path Research Articles

Engineering of interfacial electric field by g-C3N4/ZnSnO3 heterojunction for excellent photocatalytic applications

The heterojunction of 2D g-C3N4 thin nanosheets and double-shelled ZnSnO3 nanocubes was prepared via a reliable, convenient, and cost-effective technique to achieve efficient photocatalytic activity. The unique double-layered structure of ZnSnO3 helps to absorb more visible light and provides a shorter diffusion path for charge carriers. The integration of some wrapped g-C3N4 nanosheets to the outer layer of ZnSnO3 increases the multiple active sites and specific surface area (SBET) to boost the photocatalytic reaction. The synergistic effect of heterojunction and oxygen vacancies effectively stimulates the generation and spatial charge separation. Furthermore, as-synthesized 2D/3D heterostructure develops an interfacial electric field that plays an efficient role in charge migration and enhances the redox ability of the material. The degradation efficiency for MB (99.5 %, within 30 mins), TC (98.2 %, within 120 mins), H2 production rate (1799 μmol g−1 h−1) and CO evolution rate (23.6 μmol g−1 h−1) confirms the excellent performance of multifunctional photocatalyst. Additionally, DFT calculations of electronic band structure and density of states are in excellent agreement with experimental results. This work highlights the new perspective on designing suitable nanostructures for photocatalytic applications.

Design a novel mixed-ligand Ni-MOF/MWCNT nanocomposite to enhance the electrochemical performance of supercapacitors

Metal-organic frameworks (MOFs) have garnered considerable interest for supercapacitors as electrode materials. Although MOFs possess large pore sizes and high specific surface areas, most MOFs face major challenges due to their inferior stability and low electronic conductivity. In this study, we synthesized Ni-MOF/MWCNT nanocomposite using a mixed-ligand approach through hydrothermal method to provide more redox reaction sites, facilitate ion diffusion, increase the stability, and electronic conductivity of the electrode. Benzoic acid (BA) has partially replaced Benzene-1,3,5-tricarboxylic acid (BTC). BTC has been used to shape Ni-MOF nanosheets into flower-like microspheres, which can reduce the electron/ion diffusion path. The introduction of BA and combination of MWCNT and Ni-MOF result in high electric conductivity. Furthermore, the combination of two organic ligands, and the synergistic effect of MWCNTs and Ni-based MOFs lead to excellent electrochemical performance. The prepared Ni-MOF/MWCNT nanocomposite shows an outstanding capacitance of 900 F g−1 at 0.5 A g−1 and excellent cycling stability with 82 % capacity etention over 1000 cycles. This study presents an innovative strategy for enhancing energy storage performance.

Zr‐MOF nanosheets featuring benzothiadiazoles enable efficient visible light driven photooxidation of sulfides and amines

Ultrathin zirconium‐based metal–organic framework (MOF) nanosheets, embedded with photochromic units, are expected to be highly efficient heterogeneous photocatalysts, thanks to their rich catalytic sites, short diffusion paths, and effective separation of photogenerated charge carriers. Herein, we reported the synthesis of novel Zr‐MOF nanosheets (Zr‐BTDB) through a solvothermal synthesis that integrates benzothiadiazole (BTz) as a photochromic moiety within the framework of MOF. The Zr‐BTDB nanosheets processes a [Zr12(μ3‐O)8(μ3‐OH)8(μ2‐OH)6] cluster with hcp topology. Importantly, Zr‐BTDB nanosheets exhibit excellent photocatalytic activity for the photooxidation of sulfides and amines at room temperature under blue light irradiation. Notably, these nanosheets maintain their photocatalytic activity and selectivity for up to five cycles without significant loss of activity and crystallinity. Systematical catalytic reactions revealed that the Zr‐BTDB nanosheets enable the generation of singlet oxygen (1O2) and superoxide radical (O2•–) under visible light irradiation, which is critical reactive oxygen species for the photooxidation of sulfides and benzylamines. Our work represents a straightforward route for the preparation of ultrathin, water stable, and visible‐light‐activated Zr‐MOF nanosheets, offering new potentials for the selective photooxidation of sulfides and amines in an eco‐friendly way.

Hierarchical microstructure changes of oriented poly(vinylidene fluoride) foam via supercritical carbon dioxide with increased piezoelectric performance

Light weight poly (vinylidene fluoride) (PVDF) has attracted wide attention for energy supply. In this work, oriented PVDF foams were prepared using supercritical carbon dioxide (CO2) physical foaming associated with a constraint mold. The corresponding micro-nanostructures and electrical performances were researched comprehensively. It reveals that the cell structure and molecular chains of PVDF foams are oriented due to the limitation of gas diffusion paths. Because of the realization of uniaxial stretching during cell growth, the β phase content is increased. Besides, after foaming, the regularity of the chain segments in amorphous region is improved, which is caused by the decrease in the quantity of free-volume cavities. The 1D-149 °C oriented PVDF foam exhibits a high voltage output (8 V), due to the ultralow dielectric constant (1.8) and high compressive strength. This study provides a theoretical foundation for the design of oriented PVDF foams, showing the potential of energy collector.

Effect of the matrix volume fraction on the oxidation resistance of porous CVI-processed C/C composites

The correlation between the amount of chemical vapor infiltrated matrix inside porous C/C composites and their resistance to oxidation was investigated. Three C/C samples with homogeneous matrix fractions from 17% to 59% were oxidized in a thermogravimetric apparatus where a diffusion-control regime was reached. The results showed that the materials effective kinetics are proportional to their initial geometric density. With a tripled matrix content, the recession rate dropped by 50% and the depth affected by oxidation fell by 34%. A high matrix fraction was proved to favor the smallest pore sizes and to increase the tortuosity of the diffusion paths.

Contribution of Sc doping to the growth and adhesion of alumina scale on AlCoCrFeNi high-entropy alloy

Equimolar AlCoCrFeNi high-entropy alloy (HEA) often experiences serious oxidation degradation despite its superior mechanical properties at elevated temperatures. Herein, we reveal that minor Sc addition can enhance the oxidation resistance of AlCoCrFeNi HEA at 1100 °C, and the microstructure and oxidation properties for (AlCoCrFeNi)100−xScx HEAs (Sc-0, Sc-0.1, Sc-0.5 and Sc-1) are evaluated. Except for the original A2 + B2 phases, the Laves phase is found with increasing Sc addition. Moderate Sc addition is beneficial for interface adhesion by lowering the driving force for scale spallation and enhancing the interface toughness, and excessive Sc addition, however, results in serious internal oxidation due to the generation of Sc2O3 stringers as the high diffusivity paths for inward O ions. It is also proved that enhancing the interface toughness is more beneficial to improve the oxidation resistance compared to reducing scale growth rate. Our results can offer guidance for designing advanced alloys with excellent oxidation resistance.

Advancing Plastic Recycling: A Review on the Synthesis and Applications of Hierarchical Zeolites in Waste Plastic Hydrocracking

The extensive use of plastics has led to a significant environmental threat due to the generation of waste plastic, which has shown significant challenges during recycling. The catalytic hydrocracking route, however, is viewed as a key strategy to manage this fossil-fuel-derived waste into plastic-derived fuels with lower carbon emissions. Despite numerous efforts to identify an effective bi-functional catalyst, especially metal-loaded zeolites, the high-performing zeolite for hydrocracking plastics has yet to be synthesized. This is due to the microporous nature of zeolite, which results in the diffusional limitations of bulkier polymer molecules entering the structure and reducing the overall cracking of plastic and catalyst cycle time. These constraints can be overcome by developing hierarchical zeolites that feature shorter diffusion paths and larger pore sizes, facilitating the movement of bulky polymer molecules. However, if the hierarchical modification process of zeolites is not controlled, it can lead to the synthesis of hierarchical zeolites with compromised functionality or structural integrity, resulting in reduced conversion for the hydrocracking of plastics. Therefore, we provide an overview of various methods for synthesizing hierarchical zeolites, emphasizing significant advancements over the past two decades in developing innovative strategies to introduce additional pore systems. However, the objective of this review is to study the various synthesis approaches based on their effectiveness while developing a clear link between the optimized preparation methods and the structure-activity relationship of the resulting hierarchical zeolites used for the hydrocracking of plastics.

Stable Hierarchical Porous Heterostructure Ni2P/NC@CoNi2S4 Fabricated via the NiCo-LDH Template Strategy for High-Performance Supercapacitors.

Transition metal phosphide/sulfide (TMP/TMS) heterostructures are attractive supercapacitor electrode materials due to their rapid redox reaction kinetics. However, the limited active sites and weak interfacial interactions result in undesirable electrochemical performance. Herein, based on constructing the NiCo-LDH template on Ni-MOF-derived Ni2P/NC, Ni2P/NC@CoNi2S4 with a porous heterostructure is fabricated by sulfurizing the intermediate and is used for supercapacitors. The exposed Ni sites in the phosphating-obtained Ni2P/NC coordinate with OH- to in situ form an intimate-connected Ni2P/NC@NiCo-LDH, and the CoNi2S4 nanosheets retaining the original cross-linked structure of NiCo-LDH integrate the porous carbon skeleton of Ni2P/NC to yield a hierarchical pore structure with rich electroactive sites. The conducting carbon backbone and the intense electronic interactions at the interface accelerate electron transfer, and the hierarchical pores offer sufficient ion diffusion paths to accelerate redox reactions. These confer Ni2P/NC@CoNi2S4 with a high specific capacitance of 2499 F·g-1 at 1 A·g-1. The NiCo-LDH template producing a tight interfacial connection, significantly enhances the stability of the heterostructure, leading to a 91.89% capacitance retention after 10,000 cycles. Moreover, the fabricated Ni2P/NC@CoNi2S4//NC asymmetric supercapacitor exhibits an excellent energy density of 73.68 Wh kg-1 at a power density of 700 W kg-1, superior to most reported composites of TMPs or TMSs.

The diffusion path and influencing factors of shrimp farming technology

Aquatic products have played an increasingly important role in residents’ diets, with improved production capacity and living standards in recent years. Accelerating the organic diffusion of aquaculture technology is an effective way to increase production. Taking the example of South American white shrimp aquaculture, this article combines carbon emissions and aquaculture cost benefits. By using data from South American white shrimp aquaculture in Hebei, Shandong, and Jiangsu Province in China from 2016 to 2021, the article innovatively considers aquaculture cycle carbon emissions as non-expected output, constructs a non-expected SBM-DEA super-efficiency model to evaluate the comprehensive efficiency of two aquaculture technologies, and analyzes the influencing factors of the diffusion of shrimp culture technology through case studies. The research results show that the comprehensive efficiency of factory-based aquaculture technology is generally better than pond-based aquaculture, but carbon emissions are higher in the factory model. The main factors affecting the diffusion of factory-based technology are policy support, social networks, farmers’ own situations, and technological attributes.

A Novel Hydrated Iron Vanadate Cathode Material for Advanced Aqueous Nickel-Ion Batteries.

Aqueous nickel-ion batteries (ANIBs) as an emerging energy storage device attracted much attention owing to their multielectron redox reaction and dendrite-free Ni anode, yet their development is hindered by the divalent properties of Ni2+ and the lack of suitable cathode materials. Herein, a hydrated iron vanadate (Fe2V3O10.5∙1.5H2O, FOH) with a preferred orientation along the (200) plane is innovatively proposed and used as cathode material for ANIBs. The FOH cathode exhibits a remarkable capacity of 129.3 mAh g-1 at 50mA g-1 and a super-high capacity retention of 95% at 500mA g-1 after 700 cycles. The desirable Ni2+ storage capacity of FOH can be attributed to the preferentially oriented and tunnel structures, which offer abundant reaction active planes and a broad Ni2+ diffusion path, the abundant vacancies and high specific surface area further increase ion storage sites and accelerate ion diffusion in the FOH lattice. Furthermore, the Ni2+ storage mechanism and structural evolution in the FOH cathode are explored through ex situ XRD, ex situ Raman, ex situ XPS and other ex situ characteristics. This work opens a new way for designing novel cathode materials to promote the development of ANIBs.

Simultaneous treatment of trace pollutant and compound pollution using an effective n-ZnO@p-LaFeO3/3DOM SiO2 photocatalyst

To confront the complex challenges of removing trace and compound pollutants from wastewater, this research presents a novel photocatalyst, n-ZnO@p-LaFeO3/3DOM SiO2. Powered by visible light, this catalyst combines lanthanum ferrite and zinc oxide within a three-dimensional ordered macroporous silica framework. The 3DOM structure’s high surface area and porosity effectively concentrate pollutants, enhancing their interactions with reactive oxygen species (ROS) and notably reducing the ROS diffusion path. Impressively, it achieves over 96.5 % removal rates for both bisphenol A (BPA) and hexavalent chromium (Cr(VI)) at concentrations as low as 0.2 mg·L−1 within an hour. This study also discovers a synergistic effect in simultaneously oxidizing BPA and reducing Cr(VI). Moreover, it investigates the underlying mechanism, focusing on ROS generation and the crucial role of adsorption in the photocatalytic process. This study positions the presented photocatalyst as a promising solution to the intricate challenges of advanced oxidation processes (AOPs), showcasing an efficient strategy for comprehensive wastewater treatment.

Vanadium sulfide decorated at carbon matrix as anode materials for “fast-charging” lithium-ion batteries

Vanadium sulfide is considered a promising electrode material for achieving rapid lithium storage ascribing to its high specific capacity, unique crystal structure, and abundant valence states. Unfortunately, the structural collapse induced by volume expansion during charging and discharging is the key factor affecting rapid lithium storage. This article prepares composite materials with different morphologies through a strategy of decorating vanadium sulfide at carbon matrix. Among them, graphene oxide modified vanadium tetrasulfide composite materials with three-dimensional conductive networks exhibit excellent electrochemical performance. When the current density is 50 mA g−1, the discharging specific capacity reaches 1, 560 mAh g−1. After 2, 500 cycles at a high current density of 10, 000 mA g−1, the specific capacity is about 188 mAh g−1 with charging time of approximately 70 s. GITT testing indicates that the order of magnitude of the logarithm of the initial diffusion coefficient is 10−11 cm2 s−1 owing to the three-dimensional porous conductive network, which not only shortens ion diffusion path but also provides more active sites for lithium-ion storage, rendering it a promising anode material for “fast-charging” lithium-ion batteries.

Enhanced performance of graphene-incorporated electrodes for solid-state lithium-sulfur batteries through facilitated ionic diffusion pathways

Significant progress has been achieved in advancing all-solid-state lithium-sulfur batteries through the development of sulfide solid electrolytes. Nonetheless, a challenge lies in creating a percolated ion–electron conduction path with intimate contact between charge carriers throughout the cathode which is crucial for enhancing overall efficiency and addressing issues related to slow kinetics and impedance during battery operation. This study introduces a framework elucidating how the integration of graphene enhances electrode performance by refining ionic diffusion pathways. An idealized ionic diffusion pathway characterized by a continuous ionic network, facilitating minimum diffusion distances, is proposed. Through a parametric study substituting portions of ionic and electronic conductive agents with graphene, the impact on total ionic and electronic conductivity of positive electrodes was comprehended. The findings underscore the critical role of optimum graphene content, which fills the gaps between ionic conductive materials and creates the shortest diffusion paths for ions and electrons. While incorporating graphene into cathode electrodes is not novel, it is noteworthy that graphene, as a mixed ion–electron conductive material, significantly enhances ion mobility due to its 2D structure, addressing a crucial aspect of cathode performance. Upon achieving optimum composite formulation, empirical findings demonstrate substantial performance improvement, including a 17.7% increase in initial capacity and a remarkable 21% enhancement in capacity retention compared to electrodes without graphene.

Effects of ionic strength and bentonite ratio on the migration of Cr(VI) in clayey soil-bentonite engineered barrier.

Soil-bentonite (S-B) barriers have been widely used for heavy metal pollution containment. This study conducted batch adsorption tests and diffusion-through tests to evaluate how ionic strength and bentonite ratio influence the migration of Cr(VI) in natural clay-bentonite mixtures. The test results indicated that the adsorption of Cr(VI) exhibited an obvious anion adsorption effect, the pH of the soil mixture increased with the addition of bentonite, resulting in a decrease in the positive surface charge. This change led to a decrease in Cr(VI) adsorption capacity, from 775.19 mg/kg for pure clay to 378 mg/kg for mixture samples with excessive bentonite. Furthermore, as the ionic strength increases from 0 to 0.1 M, the Cr(VI) adsorption capacity increases slightly due to the weakening of electrostatic repulsion on the clay particle surface, but the effective diffusion coefficient (De) increases by 21.97%. The compression of the diffusion double layer (DDL) under high ionic strength conditions enlarges the diffusion path and enhances the migration of Cr(VI) through the pore flow paths. Moreover, hydrated bentonite effectively fills the interaggregate pores of natural clay, thus creating narrower and more tortuous flow paths. However, excessive bentonite increases the pH value and pore volume, resulting in changes to the soil microstructure and disrupting the continuous skeleton of natural clay, which is unfavorable for Cr(VI) containment. Based on the study of the Cr(VI) contaminated site, a bentonite ratio of 2:10 is recommended for optimal natural performance of the natural clay-bentonite barrier.

The acceptance of digital intelligence technology in megaproject organisations from the perspective of innovation diffusion

ABSTRACT To investigate the mechanism of employee acceptance of digital intelligence technology under technological innovation change in megaproject organisations, this study clarifies the mechanism of technological innovation diffusion in Chinese megaproject contexts. By constructing a multi-layer dynamic theoretical model of megaproject employee acceptance research, the study explores the interaction effects of multiple factors at the organisational level in the innovation diffusion process and the mechanisms of employees’ willingness to accept digital intelligence technologies. The results show that: the organisational level has a greater influence on the pre- and mid-term diffusion of innovation; the technological level gradually increases its influence on employees’ individual acceptance at the stage of innovation awareness formation; and the environmental level helps form the initial acceptance attitude. The individual level in the later stages of innovation diffusion strongly influences employees’ acceptance. The different types of megaprojects moderate the organisational model, while the interference effect of the innovation type of digital intelligence technology is not significant. The innovation of the study lies in analyzing the mechanism of innovation diffusion in the context of megaprojects along the path of innovation diffusion and exploring the interplay between organisational and individual dimensions on individual employees’ willingness to accept.

Exploring threshold of Al-impurities towards high-performance Al-doped Regenerated LiCoO2

Direct regeneration, as the main recycling manner, displays the short-process and high economic value, which has been devoted to considerable attentions. Limited by the existed pre-treatments, there are still some Al-impurities of spent material, resulting in the unstable electrochemical properties of regenerated material, meanwhile the excessive removal of Al-impurities brings the risk of regeneration cost. Thus, exploring the threshold reference of Al-impurities is urgent for regeneration of spent materials. Herein, through the introduction of Al2O3 with different content, spent LiCoO2 were successfully regenerated, displaying the evolution of physical-chemical properties. With suitable Al adding (0.02 wt.%), the broadening layer distance and storage space are found. As a cathode, the as-optimized sample shows a capacity of 172.7 mAh g−1 at 0.2 C, and the capacity retention was 84 % after 500 cycles at 5.0 C, even better than Al-impurity-free regenerated sample. Supported by the detailed kinetic analysis, it could be deduced that, suitable Al-introduction is beneficial for the fast insertion/extraction of ions, meanwhile too excess adding could bring about the blocking of diffusion paths and by-production surface stacking. Given this, this work is expected to shed light on the physical-chemical effect of Al-impurities, meanwhile offering the threshold reference for Al-doping content in practical regenerated industry.

Interlayer-confined strategy to modulate alkaline reaction microenvironment for in-situ degradation of ofloxacin

In advanced oxidation processes designed for the mineralization of organic contaminants, the acidic microenvironment in the peroxymonosulfate (PMS) activation system poses a major threat to the stability of active species. In this study, we developed a low-cost Co-Mg–layered double hydroxide (LDH) structure with an OH−-enriched, interlayer-confined alkaline microenvironment around Co sites. This structure exhibited enhanced surface availability and a short reactant diffusion path, which accelerated proton migration and regulated local pH at the slipping plane. Theoretical calculations revealed that CoMg-LDH exhibited high catalytic activity for PMS cleavage and generated high-valence Co-oxo (Co(IV)=O) species in this specific microenvironment. At a natural pH, the optimized system achieved 100 % removal efficiency of the target pollutant (ofloxacin), with negligible Co leaching. It also demonstrated stability in long-term experiments and effectively purified hospital wastewater. Overall, this study provides valuable insights into the in-situ degradation of contaminants through self-regulating catalytic systems.

Enhancing multi-channel electrode structures in ceramic fuel cells: Influence of channel geometry on mass transport and electrochemical performance

Solid oxide fuel cell (SOFC) is a promising electrochemical power generation technology that contributes to the decarbonization of the energy field. The electrode-supported design enables the use of thinner electrolytes, but inevitably brings additional gas diffusion resistance, which in turn leads to higher anodic concentration polarization. Therefore, additional structural design of the electrodes is necessary to ensure efficient operation and mass transport resistance minimization. In this study, anode-supported micro-tubular SOFCs with different multi-channel geometries have been attempted, during which samples with 4 channels exhibit unique elliptical structure due to meticulous manipulation. In addition, the 4-channel samples have been compared to the single-channel and 7-channel counterparts, exploring the influential mechanism of the anode micro-structure on gas transfer and electrochemical performances. The study found that the 4-channel cell has the best geometric controllability, with its minimum gas diffusion path reduced to below 50 μm, such thin electrochemical active region (EAR) accounts for >50 % of the entire external surface. Efficient utilization of the geometric surface area considerably facilitates the fuel transport to reach anode/electrolyte interface. By enhancing the mass transport efficiency, the maximum power density of the 4-channel cell reached 1.40 W cm−2 (750 °C), which is 22.8 % and 102.9 % higher than that of the 7-channel and single-channel cells under the same conditions. The highly efficient anode design additionally exhibited exceptional structural integrity and mechanical robustness, thereby ensuring the steady operation of the cell.

Comparative study of nudged elastic band and molecular dynamics methods for diffusion kinetics in solid-state electrolytes

Abstract Considerable efforts are being made to transition current lithium-ion and sodium-ion batteries towards the use of solid-state electrolytes. Computational methods, specifically nudged elastic band (NEB) and molecular dynamics (MD) methods, provide powerful tools for the design of solid-state electrolytes. The MD method is usually the choice for studying the materials involving complex multiple diffusion paths or having disordered structures. However, it relies on simulations at temperatures much higher than working temperature. This paper studies the reliability of the MD method using the system of Na diffusion in MgO as a benchmark. We carefully study the convergence behavior of the MD method and demonstrate that total effective simulation time of 12 ns can converge the calculated diffusion barrier to about 0.01 eV. The calculated diffusion barrier is 0.31 eV from both methods. The diffusion coefficients at room temperature are 4.3×10-9 and 2.2×10-9 cm2/s, respectively, from the NEB and MD methods. Our results justify the reliability of the MD method, even though high temperature simulations have to be employed to overcome the limitation on simulation time.

Constructing a Cr-Substituted Co-Free Li-Rich Ternary Cathode with a Spinel-Layered Biphase Interface.

Lithium-rich manganese-based layered oxides (LRMOs) have recently attracted enormous attention on account of their remarkably big capacity and high working voltage. However, some inevitable inherent drawbacks impede their wide-scale commercial application. Herein, a kind of Cr-containing Co-free LRMO with a topical spinel phase (Li1.2Mn0.54Ni0.13Cr0.13O2) has been put forward. It has been found that the high valence of Cr6+ can reduce the Li+ ion content and induce the formation of a local spinel phase by combining more Li+ ions, which is beneficial to eliminate the phase boundary between the spinel phase and the bulk phase of the LRMO material, thus dramatically avoiding phase separation during the cycling process. In addition, the introduction of Cr can also expand the layer spacing and construct a stronger Cr-O bond compared with Mn-O, which enables to combine the transition metal (TM) slab to prevent the migration of TM ions and the transformation of the bulk phase to the spinel phase. Simultaneously, the synergistic effect of the successfully constructed spinel-layered biphase interface and the strong Cr-O bond can effectively impede the escape of lattice oxygen during the initial activation process of Li2MnO3 and provide the fast diffusion path for Li+ ion transmission, thus further reinforcing the configurable stability. Besides, Cr-LRMO presents an ultrahigh first discharge specific capacity of 310 mAh g-1, an initial Coulombic efficiency of as high as 92.09%, a good cycling stability (a capacity retention of 94.70% after 100 cycles at 1C), and a small voltage decay (3.655 mV per cycle), as well as a good rate capacity (up to 165.88 mAh g-1 at 5C).