Gas-solid Reaction Research Articles

Thermochemical energy storage with the solid-gas reaction of SrCO3 improved with CaCO3

Abstract In the context of thermochemical energy storage (TCES) for concentrating solar power (CSP) applications, metal carbonates’ reversible calcination and carbonation are gaining prominence, particularly in the SrCO3/SrO system. This system is notable for its high theoretical energy density of 10.61 GJ/m³ and operational temperatures up to 1,200 °C. However, like the CaCO3/CaO system, SrO experiences a significant drop in reactivity during cycling due to sintering and agglomeration of particles. In this work is proposed that the conversion effective will be improved by mixing the strontium carbonate with calcium carbonate. The best mix found was 80/20 SrCO3/CaCO3 with the operating parameters of calcination-carbonation temperatures of 1,200 °C and 900 °C, respectively. This reaction has a notably better stable conversion rate than pure strontium carbonate. The study was carried out using thermogravimetry analysis. The mixture was subjected to 9 cycles, and for the ninth cycle, there was an effective conversion of 33.14 %, which, compared to pure SrCO3, was 2.33 %; that was improved noticeably during the carbonation process. There was an increase in the percentage effective conversion of 30.81 %. Volumetric energy density was reduced from 6.93 to 2.81 GJ/m3 in the first and after nine cycles. The XRD analysis of the unprocessed mixture after 4 and 9 cycles showed no formation of new or secondary compounds, only the expected compounds: SrO, SrCO3, CaO, and CaCO3. This important change is explained during the carbonation looping because the CaO remains encapsulated in the SrCO3 and does not react completely at 900 °C. As a hypothesis, this encapsulation delays the sintering of the SrCO3. Using a T carb = 850 °C promotes the carbonation of CaO. By promoting CaO to react, the CaO encapsulated is released rapidly, and the material was sintering faster than the T carb = 900 °C. Comparing the seventh cycle at a T carb = 900 and 850 °C, it is observed that the effective conversion decreases from 0.4431 to 0.4202 and, in the same proportion, the volumetric energy density.

Vitalizing Perovskite Oxide-Based Acetone Sensors with Metal-Organic Framework-Derived Heterogeneous Oxide Catalysts.

Perovskite oxides are promising candidates for chemiresistive-type gas sensors owing to their exceptional thermal and chemical stability during solid-gas reactions. However, perovskites suffer from critical issues such as low surface area and poor surface activity, which negatively influence the sensing characteristics. While metal nanoparticles can be incorporated in perovskites to improve their reactivity, the fundamental incompatibility between catalytic metals and perovskite oxides often leads to substantial structural degradation as well as phase instability. Herein, we overcome this challenge through the introduction of an intermediary phase that forms coherent interfaces with both the perovskite phase and catalyst metals. Specifically, we present the case study of p-type La0.8Ca0.2Fe0.98Pt0.02O3 perovskite, whose hole accumulation layer was modulated by the incorporation of metal-organic framework (MOF)-derived n-type α-Fe2O3 nanoparticles decorated with highly dispersed Pt catalysts. The resulting composite exhibited significantly improved surface activity over the nonmodified La0.8Ca0.2FeO3 perovskite, leading to exceptional chemiresistive sensing performance toward acetone gas (Rg/Ra = 39.8 toward 10 ppm of acetone at 250 °C) with high cross-sensitivity against interfering gases. Importantly, our findings reaffirm the critical influence of interfacial engineering in facilitating surface chemical reactions on perovskite oxides and, by doing so, effectively provide a general synthetic guideline to the design of perovskite-based chemiresistors.

Rational design of Z-scheme configured polymeric carbon nitride-decorated ZnWO4 nanofibers for enhanced visible-light-driven photodegradation of antibiotics

In this study, a Z-scheme heterostructure was meticulously engineered between zinc tungstate (ZnWO4) nanofibers and polymeric carbon nitride (PCN) nanosheets to augment the photocatalytic degradation of tetracycline (TC) under visible light irradiation. A cohesively integrated PCN/ZnWO4 photocatalyst structure was synthesized through an in-situ gas-solid reaction. The quantity and spatial distribution of PCN nanosheets were modulated by fine-tuning the gas precursor and reaction parameters. Relative to pristine ZnWO4 nanofibers and PCN photocatalysts, the distinct three-dimensional PCN/ZnWO4 heterostructure manifests a notable enhancement in photocatalytic performance, attributed to its plethora of active sites and a Z-scheme configuration that bolsters charge separation efficiency, achieving a tetracycline degradation rate of 95.4% upon exposure to simulated sunlight for 160 minutes. The employment of gas-solid reaction as a design paradigm pioneers a fresh paradigm in the strategic assembly of Z-scheme heterostructured photocatalysts, thereby illuminating a promising pathway for advancements in environmental remediation technologies.

In-Situ Construction of Functional Multi-Dimensional MXene-based Composites Directly from MAX Phases through Gas-Solid Reactions.

The weak bonding of A atoms with MX layers in MAX phases not only enables the selective etching of A layers for MXene preparation but brings about the chance to construct A derivatives/MXene composites via in situ conversion. Here, a facile and general gas-solid reaction systems are elegantly devised to construct multi-dimensional MXene based composites including AlF3 nanorods/MXene, AlF3 nanocrystals/MXene, amorphous AlF3/MXene, A filled carbon nanotubes/MXene, layered metal chalcogenides/MXene, MOF/MXene, and so on. The intrinsic effect mechanism of interlayer confinement towards crystal growth, catalytic behavior, van der Waals-heterostructure construction and coordination reaction are rationally put forward. The tight interface combination and synergistic effect from distinct components make them promising active materials for electrochemical applications. More particularly, the AlF3 nanorods/Nb2C MXene demonstrate bi-directional catalytic activity toward the conversion between Li2S and lithium polysulfides, which alleviates the shuttle effect in lithium-sulfur batteries.

D-Electrons of Platinum Alloy Steering CO Pathway for Low-Charge Potential Li-CO2 Batteries.

Aprotic Li-CO2 batteries suffer from sluggish solid-solid co-oxidation kinetics of C and Li2CO3, requiring extremely high charging potentials and leading to serious side reactions and poor energy efficiency. Herein, we introduce a novel approach to address these challenges by modulating the reaction pathway with tailored Pt d-electrons and develop an aprotic Li-CO2 battery with CO and Li2CO3 as the main discharge products. Note that the gas-solid co-oxidation reaction between CO and Li2CO3 is both kinetically and thermodynamically more favorable. Consequently, the Li-CO2 batteries with CoPt alloy-supported on nitrogen-doped carbon nanofiber (CoPt@NCNF) cathode exhibit a charging potential of 2.89 V at 50 μA cm-2, which is the lowest charging potential to date. Moreover, the CoPt@NCNF cathode also shows exceptional cycling stability (218 cycles at 50 μA cm-2) and high energy efficiency up to 74.6 %. Comprehensive experiments and theoretical calculations reveal that the lowered d-band center of CoPt alloy effectively promotes CO desorption and inhibits further CO reduction to C. This work provides promising insights into developing efficient and CO-selective Li-CO2 batteries.

Coupled heat transfer and chemical kinetics in a calcium oxide/hydroxide fixed bed thermochemical energy storage reactor

Among energy storage technologies, thermochemical heat storage despite its unique advantages, remains at a nascent state due to varied technical challenges. One of the key unknowns in the otherwise well-studied calcium oxide/hydroxide chemistry, is a lack of understanding of the possible output power profiles. Here, we investigate the theoretical power output from a fixed-bed, modular, honeycomb-geometry thermochemical energy storage (TCS) reactor based on a calcium oxide/hydroxide, using finite element modeling of heat transfer coupled with reaction kinetics. We calculate the extent of reaction and temperature profiles in a lattice of honeycomb cells that make up the bed, while varying heat transfer related parameters. We find that the size of the unit cell can limit energy discharge, for example, increasing the time to completion for the reaction to ∼7 hours as the cell size increases to 6 cm, even though the reaction kinetics is fast at ∼2 mins. The time constant of the transient power profile increases by a factor of ∼4 as the cell size increases by a factor of ∼3, when considering cells in the nominal size range 2–6 cm. Besides cell size, we investigate how the power profile is affected by the following parameters: the thermal conductivity of the bed, the initial temperature, the material of the cell wall and the heat transfer coefficient of external flows. In particular, we identify the combination of parameters that can vary the power profile on demand to operate the same reactor as either a thermal capacitor or alternately, a thermal battery. This work informs future design possibilities with oxide-hydroxide, solid–gas reaction TCS and provides insight into critical heat transfer parameters.

State of the art on solid–gas sorption based long-term thermochemical energy storage

Solid-gas sorption thermochemical heat storage technology is an innovative and promising solution for storing heat over long periods. The review focuses on the construction of composite sorption thermochemical heat storage materials and binary mixed salt materials with porous matrix as the supporting materials, which can further improve the hydration rate and cycle stability of single hydrated salt. Furthermore, the heat storage capabilities of the metal halide/ammonia working pair make it suitable for extreme environments, surpassing the limitations of water-based working pairs in terms of low-temperature adaptability. It is worth noting that common solid–gas reactors and measures to enhance heat and mass transfer are also reviewed. Meanwhile, the efficient open and closed heat storage systems and their optimization schemes are introduced, and the feasibility of the practical operation of the heat storage systems is evaluated comprehensively from the technical and economic perspectives, and the future research challenges are prospected.

Direct fabrication of polycrystalline γ-alumina nanochains-supported Pt nanoparticles on macroscopic ceramic substrates

We report the direct fabrication of polycrystalline γ-Al2O3 nanochains-supported Pt nanoparticles on macroscopic substrates, such as monolithic honeycombs and porous disc-typed ceramics, via chemical vapor deposition. We also investigate solid-gas reactions between the γ-Al2O3 nanochains@Pt nanoparticles and CO using in-situ transmission electron microscopy (TEM). The SEM, TEM, STEM, and XRD patterns reveal that γ-Al2O3 nanochains, 80 nm in diameter, were uniformly formed on the surfaces of macroscopic ceramic substrates. High-resolution TEM (HTEM) images confirm the polycrystalline and kinking structures connecting the nanochains. The coating thickness of γ-Al2O3 nanochains layer is approximately 100㎛. The EDX images and XPS graphs indicate that Pt nanoparticles, 3.5 nm in diameter, are well-coated on the surfaces of the γ-Al2O3 nanochains. The uniform distribution of Pt nanoparticles is precisely controlled utilizing autogenic pressure reaction. Additionally, in-situ observation significantly highlights the physicochemical phenomena of the γ-Al2O3 nanochains@Pt nanoparticles over time under CO supply at 300°C. Coke formation was accelerated on the surface of catalysts as increase of CO partial pressure increase, while Pt nanoparticles is very stable without the migration and aggregation.

CO2 sequestration by indirect mineral carbonation of serpentine with (NH4)2SO4 as a recyclable extractant

Mineral carbonation with serpentine can offer a sustainable and safe process option for simultaneous CO2 emission reduction and utilization of nature mineral. In this study, a sustainable process for CO2 mineral sequestration was proposed by using serpentine and ammonium sulfate as feedstocks. The mixture of feedstocks was subjected to roasting with temperature ranging from 390°C to 480°C, converting magnesium into the corresponding sulfate. Then, water leaching was employed to dissolve the magnesium sulfate from the roasted samples. Finally, through a mineralization reaction, the corresponding magnesium bicarbonate was generated after sequestrating CO2. Under the optimal roasting-leaching conditions, i.e. roasting temperature of 420ºC, roasting time of 2 hours, and mass ratio of ammonium sulfate/serpentine of 3; leaching temperature of 80ºC, leaching time of 1 hour, and a liquid-to-solid ratio of 1, the magnesium extraction efficiency reached 76 %. Thermodynamics and experimental results demonstrated that during the sulfation roasting process, the products generated during roasting, magnesium sulfate and silicon dioxide, adhered to the surface of the serpentine, thus inhibiting the mass transfer process and impeding the progress of the reaction. However, the liquid-solid reaction facilitated by molten ammonium sulfate and the gas-solid reaction provided by the decomposition of ammonium salts into SO2 played a promoting role in the sulfation roasting reaction. The carbonation of sulfated serpentine results indicated that the optimal CO2 storage capacity can reach 204 kg/t serpentine.

A monolithic self-supporting ZnFe2O4/ZnO/ZnNi foam photocatalyst and application in the decomposition of gaseous benzene

Volatile organic compounds (VOCs) are major air pollutants which seriously affect ecological environment and pose threats to human health. In this investigation, a monolithic self-supporting ZnFe2O4/ZnO/ZNF(ZFO/ZnO/ZNF) photocatalyst was developed by in-situ growing ZnFe2O4 and ZnO on ZnNi foam (ZNF). Using benzene as a representative of the target gaseous contaminants, the optimal 5ZFO/ZnO/ZNF achieved a 99.8 % removal efficiency and 99.7 % mineralization efficiency within 20 min at an initial benzene concentration of 600 ppm under simulated sunlight irradiation. Moreover, this catalyst presents the lower ullage during gas–solid reaction, and thus enables durable recycling reuse of the photocatalyst, which still retains a 95.8 % benzene decomposition after 30th consecutive run. The mechanism studies reveal that the metal-mediated Z-type heterostructure of ZFO/ZnO/ZNF enhances rapid transportation of the photo-generated electrons and promotes redox potential, leading to the excellent photocatalytic oxidation activity and mineralization efficiency. This study highlights the potential of self-supporting monolithic metal-mediated catalysts and provides a key strategy for effective VOCs degradation.

Simulation analysis of gas-solid two-phase flow and reaction in a novel catalytic cracking reactor

A gas-solid two-phase flow reaction model was developed to evaluate the performance of a novel catalytic cracking reactor in the residue-to-chemicals (RTC) process. Coupled TFM, EMMS drag, and 12-lump kinetic models were employed to simulate the flow reaction process. The reaction temperature and product yields at the reactor exit aligned well with real industrial RTC reactor test results, indicating the reliability and effectiveness of the coupling model. Catalyst particles formed an internal circulation structure in the reactor, increasing the instantaneous catalyst-to-oil ratio. The reactor exhibited low axial and radial temperature gradients with higher reaction temperatures, accelerating the catalytic cracking rate and enhancing the selectivity for high-value products. The effects of the catalyst-to-oil ratio, catalyst inlet temperature, and feedstock mass flow rate on the flow reaction process were optimized. Results showed that both the catalyst-to-oil ratio and catalyst inlet temperature influenced the overall catalyst velocity distribution. Within the limit range, increasing the catalyst-to-oil ratio increased feedstock conversion, gasoline, LPG, dry gas, and coke yields, but decreased diesel yield. Conversely, increasing the feedstock mass flow rate showed opposite trends. Different trends in product yields were observed with varying inlet catalyst temperatures, with optimal product distribution at 973.15 K.

Solvent Vapor/Gas-Induced Guest Transport and Exchange of a Nonporous Organic Crystal to Construct Smart Host-Guest Energetic Materials.

Supramolecular materials with advanced properties constructed by intermolecular interactions have attracted extensive attention in many fields, such as sensing, catalysis, and biomedicine. However, in the field of energetic materials, limited by the tight-packed crystal structure of explosives and the strong intermolecular interaction forces, most supramolecular explosives can only be obtained in organic solution or under extreme external loading (high temperature/high pressure). Given the practical issues such as safety risks, operational difficulties, serious environmental pollution, and large-scale production of the existing technology, a new method of constructing host-guest explosives by solvent vapor/gas induction is proposed. This gas-solid reaction method takes advantage of the metastable properties from the explosives solvate (HNIW/ACN), and cleverly opens a fast channel for gas molecules to enter the explosives cell cavities, which results in the highly efficient preparation of the host-guest explosives (HNIW/CO2 and HNIW/N2O). The embedding of functional gas molecules greatly improves the structural stability and comprehensive performance of the explosive skeleton, and the detonation velocity of HNIW/N2O even reaches 9802 m·s-1, which is higher than that of ε-HNIW (9455 m·s-1). In addition, compared with ε-HNIW, HNIW/CO2 and HNIW/N2O exhibit high energy but low sensitivity, enhanced thermal stability, and combustion properties, which present a potential prospect in the field of energetic materials. The new method effectively overcomes the high-energy barrier of nonporous organic explosives, offering the advantages of simplicity, safety, efficiency, and environmental friendliness. This study provides a valuable pathway for constructing advanced supramolecular energetic materials, which contributes to the enrichment of supramolecular engineering systems.

A kinetic comparison between in situ hybrid microwave and conventional magnetising roasting of low-grade iron ore composite pellet

This article aims to comprehensively summarise the essential aspects of reduction kinetics in magnetising roasting of low-grade iron ore–coal composite pellets in the hybrid microwave and conventional furnace. The influence of crucial process parameters like temperature, time, and heating methods, including traditional and hybrid microwave heating, is explored. Investigating the impact of low-grade iron ore and coal quality on reduction kinetics is conducted to identify optimal heating methods for upgrading low-grade iron ore to blast furnace grade through magnetising roasting. The study uses diverse gas–solid reaction models to assess the reduction mechanism (Fe2O3 to Fe3O4). Results indicate the success of the contracting volume model for microwave heating, while conventional heating transitions from phase-boundary chemical control to diffusion control. XRD confirms magnetite dominance post-reduction, while scanning electron microscopy analysis establishes microwave crack-assisted efficiency over conventional heating for ease of reduction. A comparative study of apparent activation energy reveals the hybrid microwave method's four-fold lower (36.71 kJ/mol) than conventional resistance heating (156.19 kJ/mol). This underscores the potential of microwave heating for enhanced reduction kinetics and low-grade iron ore material processing applications.

Enhanced properties of hard metal WC-Ni processed from nanostructured powders

In this study, we investigated the effects of nanostructured composite powders (WC-Ni), nickel binder content, and sintering techniques on the morphology and mechanical properties of tungsten carbide. An alternative low-temperature gas-solid reaction route with a short reaction time was employed to produce nanostructured composite powders with 5 and 15 wt% Ni. The powders were consolidated using spark plasma sintering (SPS) and conventional vacuum furnace sintering at temperatures of 1350 °C and 1450 °C. The composite powders were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and particle size measurements. The expansion/contraction of the compacted nanocomposite powders was studied through dilatometric analysis. The composite powders exhibited a uniform distribution of Ni, in both compositions. For the WC-5 wt% Ni nanocomposite powders, the average crystallite sizes for WC and Ni were 41.6 nm and 46.2 nm, respectively. While, for the WC-15 wt% Ni nanocomposite, the crystallite sizes for WC and Ni were 45.6 and 38.4 nm. The sintered composites were evaluated through XRD, SEM, measurements of density and Vickers hardness. The enhanced sinterability of the nanostructured powders enabled their consolidation into (WC-Ni) hard metal with densities approaching the theoretical relative density of 96.07 %, even with low binder content (5 wt% Ni). This is attributed to the uniform distribution of Ni and an extensive Ni-WC interface present prior to sintering. The SPS process at 1350 °C produced sintered bodies (WC-5 wt% Ni and WC-15 wt% Ni) with higher Vickers hardness (2322 HV and 1512 HV, respectively) and superior microstructural quality compared to samples produced by conventional vacuum furnace techniques. These results demonstrated that the mechanical properties of the system WC-Ni processed by SPS are superior to those obtained by vacuum furnace. Therefore, WC-Ni hard metals processed by this approach is a promising alternative to conventional hard metals (WC-Co) for a wide range of applications.

The process optimization and exergy efficiency analysis for biogas to renewable hydrogen by chemical looping technology

The study on biogas-Chemical Looping Hydrogen Production (biogas-CLHP) highlights its potential to produce high-purity hydrogen with recycling waste bioenergy. It delves into the gas-solid reaction characteristics and optimizes crucial process parameters for the fixed-bed CLHP system. Movement rate equations for the reaction fronts of Fe2O3-Fe3O4 (Rf1), Fe3O4-FeO (Rf2), and FeO-Fe (Rf3) are formulated, aiding in clarifying CO breakthrough curves. The identified convergence temperatures (Tm) under CO and H2 atmospheres are 916 °C and 907 °C, respectively. Rf1 and Rf2 converged above Tm, which leads to the disappearance of the Fe3O4 region in oxygen carrier (OC) beds. A theoretical model for calculating the reduction solid conversion (Xaver) is established, accurately characterizing Xaver under varying reaction times, H2/CO ratios, and temperatures. By using the Particle Swarm Optimization (PSO) algorithm and thermodynamic analysis, the study determines the optimal length-radius ratio (L/r), reduction temperature (T), and H2/CO ratio (α) for the OC bed as 12.5, 916 °C, and 0.72, respectively, at which a maximum conversion ratio of 43.55 % is achieved. Based on optimal parameters, the results of Aspen simulation reveal energy and exergy efficiencies of 74.9 % and 70.8 %. Generally, this research comprehensively outlines the process dynamics, optimizes key parameters, and evaluates exergy efficiency of the biogas-CLHP system.

Ce(III) formate-derived hierarchical cerium oxide particles with icosahedral symmetry-based architectures: Effect of third level of structural hierarchy in soot and propane oxidation

The article investigates the role of architecture of complex hierarchically structured ceria and gadolinium doped ceria particles in soot combustion (solid-solid reaction) and propane oxidation (gas-solid reaction). Synthesis of hierarchical ceria mesostructures showing icosahedral symmetry-based architecture has been presented for the first time. Carefully choosing synthetic conditions allows to obtain particles with intended morphology of dodecahedron, rhombic hexecontahedron, great stellated dodecahedron, fractal-like branched great stellated dodecahedron and great dodecahemicosacron polyhedra. Twinning-based multiple branching of Ce(III) formate crystals by {101} twin orientation relation was proposed as a driving mechanism for the formation of macroparticles architecture that has been confirmed by the construction of macroparticle models using the identified twinning law. In the catalytic studies, the third level of the material organizational structure referring to shape of hierarchical macroparticles was chosen as a tested variable, while other architecture-related properties were controlled to be alike. In result, the shape of hierarchical particles plays a vital role in the catalytic soot oxidation, and architecture modulation allows the catalytic properties of the material to be enhanced through increasing the geometrical fit between ceria and soot particles. The best sample lowers temperature of half oxidation by 143 °C as compared to non-hierarchically organized ceria nanocrystals. The shape of hierarchical particles does not play leading role in gas-solid propane oxidation, but introduction of Gd dopant diversifies catalytic activity. The architecture of the particles may serve as a modifier of the catalytic activity through grain boundary engineering of gadolinium doped ceria.

Novel experimental method to simulate reduction behaviour of burden in blast furnace shaft

In order to evaluate the effects of CO and H2 for the gas–solid reaction behaviour of the ferrous burden and coke in blast furnace shaft, a near-steady-state simulation test method of the blast furnace shaft was designed. The reduction behaviour of the ferrous burden, carbon solution loss reaction under different temperatures and atmospheres, and the effect of hydrogen enrichment on the CO gas utilisation ratio were investigated. The results show that above 830 °C, the reduction degrees of different ferrous burden structures under H2 atmosphere are higher than that under CO atmosphere. Better reduction degradation behaviour could be obtained under the hydrogen-rich atmosphere. The H2O generated under H2 atmosphere could promote the carbon solution loss reaction. The solution loss ratio reaching the maximum at 950 °C. Under hydrogen-rich atmosphere, CO gas utilisation ratio increased with the increased H2 concentration due to the effects of the products H2O and CO2.

Hybrid thermochemical cycle for cold and electricity cogeneration: Experimental and numerical analyses of the process behavior and expander-reactor coupling

The valorization of waste heat to respond to the increase demand on electricity and cooling is an important energetic challenge. For this purpose, a hybrid thermochemical cycle is proposed. This discontinuous sorption cycle is based on reversible endothermic/exothermic solid–gas reactions, and it is able to recover medium grade waste heat (between 150 and 250 °C) to valorize it in a second step by providing cold production at its endothermic component and mechanical work thanks to the integration of an expander on the gas line. Moreover, the two-step operation leads to a storage functionality. This paper presents an experimental study of this new hybrid cycle prototype in different operating conditions, and a sensitivity study of the design parameters of the prototype performed through a steady state model. The experimentation shows the influence of the electrical load applied to the generator on the coupling between the expander and reactor, by affecting the rotational speed, the torque of the expander and the pressure of the reactor. The analysis of the experimental results highlighted the effect of two main limitations in the prototype: the internal leaks on the expander side (unlubricated scroll expander) and the heat transfer on the reactor side. A numerical parametric study is done on these two parameters, showing the possibility of cogenerating 125 W of mechanical power and 2.3 kW of cold for defined enhanced parameters of the prototype. These promising results prompt the next step of conducting a detailed exergetic analysis of the cycle. This analysis will aim to identify the primary sources of exergy destruction and to explore ways for reducing them by minimizing main irreversibilities in the cycle.

Fabricated ZnIn2S4/Cu2S S-scheme heterojunction with snowflake structure for boosting photocatalytic CO2 reduction in gas–solid reactor

Designing S-scheme heterojunctions has become a powerful strategy to enhance photocatalytic activity and improve the localization of catalyst surface charge. Therefore, more and more research has been devoted to S-scheme heterojunctions. In this work, we employed a simple two-step hydrothermal method to fabricate S-scheme ZnIn2S4/Cu2S (ZIS/Cu2S) heterojunctions. The results show that the composites exhibit good performance in the photoreduction of CO2 to CO and CH4. Especially, at 40 %-ZIS/Cu2S, the release rates of CO and CH4 were 13.35 μmol g−1 and 34.81 μmol g−1 under the condition of a 4 h reaction, and the selectivity of CH4 reached 80 %. In addition, the in situ FTIR test revealed that the catalyst promoted the formation of the key intermediates COOH* and CH3O* under the effect of light interaction, which was favorable to the photoreduction of CO2. This indicates that the electron transfer path of S-type not only promotes the separation of carriers for conversion but also has a strong redox ability to selectively convert CO2 to CH4, which provides some thoughts for the design of S-scheme heterojunction photocatalysts. This provides some thoughts for the design of S-scheme heterojunction photocatalysts.

Optical thermometry using efficient upconversion luminescence in Er3+ self-sensitized NaYS2 under multi-wavelength excitation

Herein, a series of Er3+ self-sensitized NaYS2 phosphors are synthesized by the solid-gas reaction method for a novel upconversion luminescence thermometer. Er3+ possesses abundant excited state energy levels in the near-infrared region, enabling efficient upconversion luminescence by absorbing different near-infrared wavelength light. Compared to 980 nm excitation, the emission intensity is enhanced by nearly an order of magnitude under 1532 nm excitation, which can be attributed to the larger absorption cross-section of 4I13/2 and stronger absorption efficiency for Er3+. Based on the luminescence intensity ratio technique, the optical thermometry behaviors of NaYS2:Er3+ under different wavelength excitation are evaluated by employing the thermally coupled energy levels of 2H11/2/4S3/2. It can be deduced that the excitation wavelength has no significant effect on the temperature sensing parameters. Compared to other typical upconversion luminescence thermometers, NaYS2:Er3+ thermometer exhibits not only excellent sensitivity performance but also high upconversion luminescence efficiency, which is expected to be applied in wide-temperature-range and highly-sensitive temperature sensing.