Gas Adsorption Research Articles

Front Cover: Mechanochemical “Cage‐on‐MOF” Strategy for Enhancing Gas Adsorption and Separation through Aperture Matching

Front Cover: Mechanochemical “Cage‐on‐MOF” Strategy for Enhancing Gas Adsorption and Separation through Aperture Matching

Mechanochemical “Cage‐on‐MOF” Strategy for Enhancing Gas Adsorption and Separation through Aperture Matching

AbstractPost‐modification of porous materials with molecular modulators has emerged as a well‐established strategy for improving gas adsorption and separation. However, a notable challenge lies in maintaining porosity and the limited applicability of the current method. In this study, we employed the mechanochemical “Cage‐on‐MOF” strategy, utilizing porous coordination cages (PCCs) with intrinsic pores and apertures as surface modulators to improve the gas adsorption and separation properties of the parent MOFs. We demonstrated the fast and facile preparation of 28 distinct MOF@PCC composites by combining 7 MOFs with 4 PCCs with varying aperture sizes and exposed functional groups through a mechanochemical reaction in 5 mins. Only the combinations of PCCs and MOFs with closely matched aperture sizes exhibited enhanced gas adsorption and separation performance. Specifically, MOF‐808@PCC‐4 exhibited a significantly increased C2H2 uptake (+64 %) and a longer CO2/C2H2 separation retention time (+40 %). MIL‐101@PCC‐4 achieved a substantial C2H2 adsorption capacity of 6.11 mmol/g. This work not only highlights the broad applicability of the mechanochemical “Cage‐on‐MOF” strategy for the functionalization of a wide range of MOFs but also establishes potential design principles for the development of hybrid porous materials with enhanced gas adsorption and separation capabilities, along with promising applications in catalysis and intracellular delivery.

Vacancy Effect on the Luminescent and Water Responsive Properties of Vacancy-Ordered Double Perovskite Derivatives.

Vacancy-ordered perovskites and derivatives represent an important subclass of hybrid metal halides with promise in applications including light emitting devices and photovoltaics. Understanding the vacancy-property relationship is crucial for designing related task-specific materials, yet research in this field remains sporadic. For the first time, we use the Connolly surface to quantitatively calculate the volume of vacancy (V□, □=vacancy) in vacancy-ordered double perovskite derivatives (VDPDs). A relationship between void fraction and the structure, photoluminescent properties and humidity stability was established based on zero-dimensional (0-D) [N(alkyl)4]2Sb□Cl5□'-type VDPDs. Compared with the more commonly studied A2M(IV)X6□-type double perovskite (A=cation, M=metal ion, X=halide), [N(alkyl)4]2Sb□Cl5□' features double vacancy sites. Our results demonstrate an inverse relationship between the photoluminescent quantum yield and V□ in 0-D VDPDs. Additionally, structural transformation from A2SbCl5 to A3Sb2Cl9 was first reported, during which the novel 'gate-opening' gas adsorption phenomenon was observed in VDPDs for the first time, as evidenced by 'S'-shaped sorption isotherms for water vapor, indicating a cation-controlled water-vapor response behavior. A mixed-cation strategy was developed to modulate the humidity stability of VDPDs. Characterized by controllable water-responsive behavior and unique 'on-off-on' luminescent switching, A2M(III)□X5□'-type materials show great promise for multi-level information anti-counterfeiting applications.

Vacancy Effect on the Luminescent and Water Responsive Properties of Vacancy‐Ordered Double Perovskite Derivatives

AbstractVacancy‐ordered perovskites and derivatives represent an important subclass of hybrid metal halides with promise in applications including light emitting devices and photovoltaics. Understanding the vacancy‐property relationship is crucial for designing related task‐specific materials, yet research in this field remains sporadic. For the first time, we use the Connolly surface to quantitatively calculate the volume of vacancy (V□, □=vacancy) in vacancy‐ordered double perovskite derivatives (VDPDs). A relationship between void fraction and the structure, photoluminescent properties and humidity stability was established based on zero‐dimensional (0‐D) [N(alkyl)4]2Sb□Cl5□′‐type VDPDs. Compared with the more commonly studied A2M(IV)X6□‐type double perovskite (A=cation, M=metal ion, X=halide), [N(alkyl)4]2Sb□Cl5□′ features double vacancy sites. Our results demonstrate an inverse relationship between the photoluminescent quantum yield and V□ in 0‐D VDPDs. Additionally, structural transformation from A2SbCl5 to A3Sb2Cl9 was first reported, during which the novel ‘gate‐opening’ gas adsorption phenomenon was observed in VDPDs for the first time, as evidenced by ‘S’‐shaped sorption isotherms for water vapor, indicating a cation‐controlled water‐vapor response behavior. A mixed‐cation strategy was developed to modulate the humidity stability of VDPDs. Characterized by controllable water‐responsive behavior and unique ‘on‐off‐on’ luminescent switching, A2M(III)□X5□′‐type materials show great promise for multi‐level information anti‐counterfeiting applications.

Silica/klucel nanocomposite as promising durable adsorbent for lead removal from industrial effluents

The removal of heavy metals, such as lead, from industrial wastewater is imperative due to their detrimental effects on both human health and the environment. This study delves into investigating the feasibility of employing a novel adsorbent, specifically a silica/klucel nanocomposite, for effectively extract lead from industrial effluents. The synthesis of this nanocomposite involved a simple and cost-effective method, combining silica nanoparticles with klucel. XRD, FTIR, E-SEM, Raman, and N2 gas adsorption at − 196 °C tools were employed to prospect the formation of silica/klucel nanocomposite. Outstandingly, treating 50 ml of 50 mg/l of lead with 10 mg of adsorbent exhibited rapid removal, which reached a maximum (95%) at 60 min contact time. The resulting composite demonstrated remarkable adsorption capabilities, primarily attributed to two factors: the expansive surface area of silica nanoparticles 139.1 m2/g and the porous structure provided by klucel. Through batch adsorption experiments, the nanocomposite’s proficiency in removing lead ions from aqueous solutions became evident. The kinetics of the adsorption process were found to adhere closely to a pseudo-second-order model, hinting at chemical adsorption as the rate-determining step. Langmuir isotherm model revealed that lead ions tend to form a monolayer on the surface of the nanocomposite and the maximum adsorption capacity (qm) was 63.938 mg/g. Additionally, the nanocomposite, exhibited notable stability and could be reused multiple times, where 65% removal efficiency was announced until the 7th cycle without significant degradation in performance. In summary, the silica/klucel nanocomposite emerges as a promising and eco-friendly adsorbent for removing lead from industrial effluents. Its efficient performance and sustainability offer a compelling solution to combat heavy metal contamination, thereby contributing to environmental preservation and human well-being.

Tailoring anisotropic ZnO/wood-structural holocellulose hybrids for dye degradation through controlled nanoinsertion

Nanostructured inorganic/wood-structural holocellulose hybrids offer new potential applications, including mechanical energy conversion, superhydrophobic materials, gas adsorption and so on. Owing to the anisotropy of wood, controlling the morphology of mineral particles inside porous holocellulose scaffold is still far from satisfactory. In this work, a homogeneous zinc oxide (ZnO) decoration inside wood-structural holocellulose scaffold was achieved while the morphology, distribution and content of ZnO micro-nano particles were controllable through changing the conditions of hydrothermal growth. The holocellulose scaffold was prepared through delignification and periodate oxidation, which is favorable for Zn2+ capture and ZnO nuclei formation because of the surface charge increased. The controlled ZnO insertion was realized by changing metal salt concentration, temperature and hydrothermal time. The obtained multilayer ZnO could provide multiple light refractions and reflections and enhance the utilization of light. Consequently, with a minor ZnO loading (15 wt%), the ZnO/wood-structural hybrids could totally degrade methyl orange and methyl blue in 6 h. This novel and scalable synthesis method shows potential for both the design and photocatalytic activity of holocellulose hybrids.

Simulation of Adsorption and Separation Behavior of Elemental Gases on Lanthanide-Based Nd-MOF

Simulation of Adsorption and Separation Behavior of Elemental Gases on Lanthanide-Based Nd-MOF

Adsorption Properties of Metal Atom (Co, V, W, Zr)-Modified MoTe2 for CO, CH3CHO, and C6H6 Gases: A DFT Study

This study investigates the adsorption characteristics of the pristine MoTe2 monolayer and the metal atom (Co, V, W, Zr)-modified MoTe2 monolayer on the hazardous gases CO, CH3CHO, and C6H6 based on the density functional theory. The adsorption mechanism was studied from the perspectives of molecular density differences, band structures, molecular orbitals, and the density of states. Research analysis showed that the changes in conductivity caused by the adsorption of different gases on the substrate were significantly different, which can be used to prepare gas sensing materials with selective sensitivity for CO, CH3CHO, and C6H6. This study lays a reliable theoretical foundation for the gas sensing analysis of toxic and hazardous gases using metal atom-modified MoTe2 materials.

A novel model of kinetics and thermodynamics for shale gas adsorption–diffusion

The study of adsorption–diffusion kinetics in shale gas reservoirs is crucial for predicting reserves and assessing production. Although some scholars have proposed adsorption–diffusion kinetics models, there are few models and interpretation methods that systematically consider Arrhenius’s thermodynamics parameters and actual adsorption gas concentration. In this study, we propose a novel model for analyzing the kinetics processes of adsorbed gas and free gas in shale. The analysis of adsorbed gas kinetics experimental data indicates a negative correlation between temperature and the adsorption–diffusion equilibrium time. Sensitivity analysis of the parameters reveals that three parameters (the diffusion activation energy, adsorption activation energy, and desorption pre-exponential factor) are positively correlated with adsorption–diffusion equilibrium time, whereas the other three parameters (the diffusion pre-exponential factor, adsorption pre-exponential factor, and desorption activation energy) are negatively correlated. Furthermore, we find that higher temperatures lead to lower concentrations of free gas at equilibrium state. Larger radius positions in spherical particles tend to reach adsorption–diffusion equilibrium earlier. Compared to the traditional diffusion kinetics model, the proposed novel model exhibits a significant lag effect in the calculated equilibrium time and more accurately describes the gas adsorption-diffusion kinetics equilibrium process.

Probing Prismatic/Basal Surfaces of Carbon Materials upon Graphitization by Gas Adsorption, TPD, and XPS

Probing Prismatic/Basal Surfaces of Carbon Materials upon Graphitization by Gas Adsorption, TPD, and XPS

Response of nano-pores and heterogeneity of tar-rich coal to microwave pyrolysis

ABSTRACT In-situ pyrolysis of tar-rich coal can alleviate the external dependence of oil and gas in China, and achieve efficient and safe exploitation of tar-rich coal. In fact, the nano-pores and heterogeneity of tar-rich coal undergo significant changes during pyrolysis, but there is currently limited research, which seriously restricts the efficient utilization of tar-rich coal. In this study, the pore and heterogeneity characteristics of tar-rich coal were studied by microwave pyrolysis experiment, gas adsorption results and multifractal theory, and the pyrolysis evolution mechanism of pores of tar-rich coal was proposed. The results show that microwave pyrolysis significantly promoted the development of nano-pores in tar-rich coal. The nano-pore size distribution of tar-rich coal after pyrolysis showed obvious multifractal characteristics, and the influence of sparse area on nano-pore size distribution was more obvious, while the nano-pore distribution heterogeneity increases initially and subsequently drops with temperature. Moreover, the development of nano-pores in tar-rich coal occurred in three stages. Stage I, the total pore volume changed little, increasing only from 0.06851 to 0.09463 ml/g, and thermal cracking is the main reason for pore development. Stage II, numerous pores were produced as a result of the pyrolysis products’ generation, and total pore volume grew rapidly increased to 0.331 ml/g. Stage III, liquid hydrocarbons and precipitated volatile products blocked nano-pores, so that the total PV began to decrease. The total pore volume was only 0.19967 ml/g at 1000°C. This study provides guidance for the investigation of pore evolution during pyrolysis and enriches the theory of in-situ pyrolysis of tar-rich coal.

Microscopic scale influence of functional groups on the displacement behavior of coalbed methane by hot humid flue gas: A molecular simulation study based on the dynamic injection process

Building upon the CO2-ECBM technology (CO2-Enhanced Coaled Methane Recovery Technology), hot flue gas injection for displacing coalbed methane has been proposed to improve methane recovery efficiency and reduce the costs associated with CO2 capture during the displacement process as well as flue gas desulfurization and denitrification at coal-fired power plants. To explore the microscopic mechanisms of displacement and the influence of functional groups, this study used Molecular Dynamics (MD) and Grand Canonical Monte Carlo (GCMC) methods with Materials Studio software to model slit pores grafted with various functional groups for gas adsorption simulations. The adsorption characteristics of eight key functional groups (-C=OCH₃, -COOH, -CH₂OH, Ar-OH, -OCH₃, -C6H6, -CH₃, -CH₂) for hot flue gas and methane were analyzed, focusing on adsorption strengths and underlying mechanisms. Simulations of the dynamic injection of hot flue gas were conducted, monitoring energy changes and methane density distribution to establish the relationship between adsorption strength and the difficulty of coalbed methane (CBM) displacement. The results indicate that in this simulation, the methane displacement efficiency using hot flue gas to displace coalbed methane exceeded 98%, demonstrating significantly better displacement performance compared to the use of pure carbon dioxide or nitrogen. Although both methane and hot flue gas show that greater interaction energy with pores makes displacement more difficult, the underlying causes differ. A comparison of the interaction energies between different functional groups and various gases reveals that oxygen-containing functional groups (-C=OCH3, -COOH, -CH2OH, Ar-OH, -OCH3) are unfavorable for the displacement of coalbed methane by wet hot flue gas, whereas aliphatic hydrocarbons (-CH3, -CH2) facilitate the displacement process.

Impact of gas adsorption of nitrogen, argon, methane, and CO2 on gas permeability in nanoporous rocks

Gas adsorption on the surface of nanoporous rocks is an important process that occurs in many applied scenarios such as shale gas production or CO2 enhanced gas recovery or storage. While there are few theoretical considerations on the effect of gas adsorption on permeability, a systematic laboratory investigation of the impact of gas adsorption on gas flow and permeability is still lacking. In this paper, permeability of four adsorptive gases, i.e., nitrogen, argon, methane, and carbon dioxide, was measured, along with helium permeability, for two nanoporous rock samples that have high and low total organic carbon (TOC) content, respectively. The measurements were conducted at a range of pore pressures from 150 to 1500 psi (1.03–10.34 MPa). Gas adsorption isotherms were also measured at the same conditions. A mathematical model that considers adsorption with specific boundary conditions for the experimental setup was used for data analysis. The results show that gas adsorption causes larger drop in pressure decay and greater retardation in pressure equilibrium. However, the reduction of permeability relative to helium (25%–46%) is similar for gases with different levels of adsorption, indicating the occurrence of single-layer adsorption for these gases. Comparison between the two samples further supports the concept of single-layer adsorption and signifies the impact of pore size on the permeability reduction due to adsorption. These new findings deepen the fundamental understanding and provide important clarification on the effect of gas adsorption on gas flow and permeability in nanoporous rocks.

Hierarchical Heterojunctions of Metal Sulfide WS2 Nanosheets/Metal Oxide In2O3 Nanofibers for an Efficient Detection of Formaldehyde

The construction of transition metal dichalcogenides (TMDs) heterojunctions for high-performance gas sensors has garnered significant attention due to their capacity to operate at low temperatures. Herein, we realize two-dimensional (2D) WS2 nanosheets in situ grown on one-dimensional (1D) In2O3 nanofibers to form heterostructures for formaldehyde (HCHO) gas sensors. Capitalizing on the p-n heterojunctions formed between WS2 and In2O3, coupled with the high surface-to-volume ratio characteristic of 1D nanostructures, the WS2/In2O3 NFs sensor demonstrated an elevated gas response of 12.6 toward 100 ppm HCHO at 140 °C, surpassing the performance of the pristine In2O3 sensor by a factor of two. Meanwhile, the sensor presents remarkable repeatability, rapid response/recovery speed, and good long-term stability. The superior sensing capabilities of WS2/In2O3 NFs heterojunction are attributed to the combined impact of the increased charge transfer and the presence of more sites for gas adsorption. The research endows a potent approach for fabricating TMD heterojunctions to significantly enhance the gas sensing properties of gas sensors at relatively low temperatures.

Optical Fiber HMS Ammonia Sensor with Cellular-like N-CQDs/MgxZn1-xO at Room Temperature.

This paper presents an optical fiber hollow malposition structure (HMS) elaborated with cellular-like N-CQDs/MgxZn1-xO for detecting ammonia (NH3) at room temperature. The gas detection was realized by combining the HMS to excite the surface evanescent field on the outer surface of the hollow core fiber (HCF) and the surface-coated cellular-like N-CQDs/MgxZn1-xO material for improving sensitivity. Experimental results demonstrate that the sensor coated with N-CQDs/Mg0.2Zn0.8O exhibits the highest sensitivity, reaching 8.9 pm/ppm, which is 11.6 times higher than that with Mg0.2Zn0.8O. Additionally, the NH3 sensor can determine a minimum concentration of 1 ppm and has response and recovery times of 6.2 and 7.1 s, respectively. Density functional theory (DFT) calculations confirm that N-CQDs reduces the bandgap of the composite material and increase the carrier concentration on its surface, thereby enhancing gas adsorption capacity. The intrinsic characteristics of the proposed sensor including small size, high sensitivity, and good stability reveal its promising prospects in detecting low concentrations of NH3.

Fractal Strategy for Improving Characterization of N2 Adsorption–Desorption in Mesopores

The current studies primarily analyze the heterogeneity and complexity of mesopore structures based on low-temperature nitrogen (N2) adsorption curves and the Frenkel–Halsey–Hill (FHH) fractal model. However, these studies ignore the fact that the low-temperature N2 desorption curve can also reflect the desorption performance of the mesopore structure. In this research, novel fractal indicators for characterizing the adsorption–desorption performance of mesopores based on the fractal dimension from the N2 adsorption curves and N2 desorption curves are proposed. The novel fractal indicators I1 and I2 are applied to evaluate the adsorption–desorption performance of mesopores with pore size 2–5 nm and pore size 5–50 nm, respectively. The fractal indicator I1 shows an increasing trend with coalification, reflecting that the gas adsorption performance of 2–5 nm mesopores is enhanced with coalification. The fractal indicator I2 exhibits a trend of first increasing and then decreasing with coalification, indicating the gas desorption performance of mesopores with pore size 5–50 nm decreases first and then increases. The proposed indicators provide novel analytical parameters for further understanding the gas adsorption–desorption mechanism of porous coal-based or carbon-based materials.

Five definitions of adsorption and their relevance to the formulation of dynamic mass balances in gas adsorption columns

Numerous dynamic mass balances in the literature that describe the adsorption of gases in a column are written in terms of actual or absolute adsorption, while unwittingly and incorrectly utilizing excess adsorption isotherms. Perhaps this is because the actual and absolute adsorption isotherms cannot be experimentally measured nor predicted without making uncertain assumptions. The objective here was to derive unambiguous relationships between actual, absolute, excess, net and column amounts adsorbed that provide a straightforward understanding of the subtle differences between these quantities and that provide a simple means for incorporating them into dynamic mass balances. For this purpose, the actual, absolute, excess, net and column amounts adsorbed (loadings) were clearly defined, along with various volumes, porosities and densities that exist inside and outside an adsorbent contained in a column with a gaseous adsorbate. These adsorption definitions and quantities were used to derive four interconversion relationships for each type of adsorption in terms of the actual loading. The resulting expressions, based on intensive properties, can be used to relate any adsorption definition to any other adsorption definition. These relationships were also used to derive five dynamic mass balances, one for each type of adsorption. The similarities and differences in the terms between each of these five dynamic mass balances were discussed, along with their applicability to real world problems. In some cases at low pressure where the isotherms do not differ appreciably, it may be approximately correct to use excess or net adsorption isotherms in a dynamic mass balance written in terms of actual or absolute adsorption. However, the extent of the incorrectness is unknown due to mass transfer effects. So, it is recommended to use the dynamic mass balance with its specific type of adsorption, most likely excess adsorption. Then, when certain assumptions are made about the adsorbing and non-adsorbing void fractions, these expressions can be readily used in adsorption process simulation.

Unraveling the Oxygen Vacancy-Performance Relationship in Perovskite Oxides at Atomic Precision via Precise Synthesis.

Understanding the fundamental effect of the oxygen vacancy atomic structure in perovskite oxides on catalytic properties remains challenging due to diverse facets, surface sites, defects, etc. in traditional powder catalysts and the inherent structural complexity. Through quantitative synthesis of tetrahedral (LaCoO2.5-T), pyramidal (LaCoO2.5-P), and octahedral (LaCoO3) epitaxial thin films as model catalysts, we demonstrate the reactivity orders of active-site geometrical configurations in oxygen-deficient perovskites during the CO oxidation model reaction: CoO4 tetrahedron > CoO6 octahedron > CoO5 pyramid. Ambient-pressure Co L-edge and O K-edge XAS spectra clarify the dynamic evolutions of active-site electronic structures during realistic catalytic processes and highlight the important roles of defect geometrical structures. In addition, in situ XAS and resonant inelastic X-ray scattering spectra and density functional theory calculations directly reveal the nature of high reactivity for CoO4 sites and that the derived shallow-acceptor defect levels in the band structure facilitate the adsorption and activation of reactive gases, resulting in more than 23-fold enhancement for catalytic reaction rates than CoO5 sites.

Promoted room temperature NH3 gas sensitivity using interstitial Na dopant and structure distortion in Fe0.2Ni0.8WO4.

The demand for gas-sensing operations with lower electrical power and guaranteed sensitivity has increased over the decades due to worsening indoor air pollution. In this report, we develop room-temperature operational NH3 gas-sensing materials, which are activated through electron doping and crystal structure distortion effect in Fe0.2Ni0.8WO4. The base material, synthesized through solid-state synthesis, involves Fe cations substitutionally located at the Ni sites of the NiWO4 crystal structure and shows no gas-sensing response at room temperature. However, doping Na into the interstitial sites of Fe0.2Ni0.8WO4 activates gas adsorption on the surface via electron donation to the cations. Additionally, the hydrothermal method used to achieve a more than 70-fold increase in the surface area of structure-distorted Na-doped Fe0.2Ni0.8WO4 powder significantly enhances gas sensitivity, resulting in a 4-times increase in NH3 gas response (Rg/Ra). Photoluminescence and XPS results indicate negligible oxygen vacancies, demonstrating that cation contributions are crucial for gas-sensing activities in Na-doped Fe0.2Ni0.8WO4. This suggests the potential for modulating gas sensitivity through carrier concentration and crystal structure distortion. These findings can be applied to the development of room-temperature operational gas-sensing materials based on the cations.

Porphyrinoid-Functionalized ZnO Nanoflowers for Visible Light-Enhanced and Selective Benzylamine Detection at Room Temperature.

Functionalization of hybrid organic molecules as layers on ZnO nanoflowers (NFs) gives an excellent combination of sensing toward visible light and vapors of various volatile organic compounds (VOCs). In this work, hybrid organic molecules functionalized ZnO NFs were utilized for the photoinduced detection of benzylamine at room temperature. The ZnO NFs were synthesized via a facile solution route and functionalized with four different porphyrin-conjugated molecules namely (i) pyrene-porphyrin (PP), (ii) pyrene- porphyrinato zinc (ZnPP), (iii) triphenylamine- porphyrin (TP) and (iv) triphenylamine- porphyrinato zinc (ZnTP). The diameter of the flower-like structure was found to be ∼3.2 μm with the thickness of petals being ∼24.1 nm. The gas adsorption performance of the functionalized ZnO NFs on light activation at room temperature was studied by using a scanning Kelvin probe (SKP) system. The improved adsorption properties of the samples can be attributed to the heterojunctions and light activation. In particular, an enhanced response of ZnTP functionalized ZnO (ZnTPZ) toward benzylamine was observed. Further, static gas sensing experiments using ZnTPZ under various concentrations (1, 3, 5, 10, 15, and 25 ppm) of benzylamine vapors both in dark and visible light conditions have exhibited a linear increase in the response. The selectively enhanced response of ZnTPZ compared to that of pristine ZnO was thus confirmed at 1 ppm of benzylamine. The sensitivity and limit of detection of the ZnTPZ sensor were calculated to be 0.0292 ppm-1 and 197 ppb, respectively. The coordination metal (Zn) has helped in effective charge transfer between benzylamine and ZnTPZ by providing additional active sites for interactions. Also, density functional theory calculations demonstrated the role of the hybrid organic molecules on the sensor surface in improving gas adsorption. Further, fresh cabbage was utilized for real sample analysis with the proposed sensor under visible light illumination conditions, and a linear response was obtained for low ppm evaluation at room temperature. Overall, the obtained results suggest the development of novel ZnTPZ-based light-activated gas sensors for low ppm benzylamine detection at room temperature. These kinds of sensors can be used to track the freshness of vegetables as they are transported from farms to commercial outlets.