Restricting Linker Rotation in Nanocages of ZIF-8 Membranes using Crown Ether "Molecular Locks" for Enhanced Propylene/Propane Separation.

ZIF-8 membranes have long been prized for their exceptional C3H6/C3H8 separation performance. On the other hand, ZIF-8 has structural flexibility, where the external pressure triggers channel expansion, potentially deteriorating the molecular sieving ability. Here, we demonstrate a reliable strategy to fine-tune the flexible pore structure of ZIF-8 by embedding crown ether within a ZIF-8 membrane. Benzo-15-crown-5 (15C5) was selected as the cavity occupant and perfectly confined in the sodalite (SOD) cage of ZIF-8. The 15C5 molecules, which have a size comparable to the nanocage, impose a spatial constraint on linker rotation, enabling the phase transition to a rigid structure in the flexible ZIF-8. The corresponding 15C5@ZIF-8 membranes achieve an ultrahigh C3H6/C3H8 selectivity of 220, outperforming that of most membranes. Unlike their flexible counterparts, the resulting membranes manifest a positive increase in the C3H6/C3H8 separation factor with elevated pressure, securing a record-high C3H6/C3H8 separation factor of 331 under 7 bar. More importantly, extraordinary separation stability was demonstrated with continuous measurement, which is highly desirable for practical applications.

Impact of yeast extract and basal salts medium on 1,4-dioxane biodegradation rates and the microorganisms involved in carbon uptake from 1,4-dioxane.

Conventional physical and chemical treatment technologies for 1,4-dioxane can be ineffective and consequently attention has focused on bioremediation. Towards this, the current research investigated the impact of basal salts medium (BSM) and yeast extract on 1,4-dioxane biodegradation rates in microcosms with different soil or sediment (agricultural soil, wetland sediment, sediment from an impacted site). Phylotypes responsible for carbon uptake from 1,4-dioxane were determined using stable isotope probing (SIP), both with and without BSM and yeast extract. Further, putative functional genes were investigated using 1) soluble di-iron monooxygenase (SDIMO) based amplicon sequencing, 2) qPCR targeting propane monooxygenase (large subunit, prmA) and 3) a predictive approach (PICRUSt2). The addition of BSM and yeast extract significantly enhanced 1,4-dioxane removal rates the agricultural soil and impacted site sediment microcosms. The phylotypes associated with carbon uptake varied across treatments and inocula. Gemmatimonas was important in the heavy SIP fractions of the wetland sediment microcosms. Unclassified Solirubacteraceae, Solirubrobacter, Pseudonocardia and RB4 were dominant in the heavy SIP fractions of the agricultural soil microcosms. The heavy SIP fractions of the impacted site microcosms were dominated by only two phylotypes, unclassified Burkholderiaceae and oc3299. SDIMO based amplicon sequencing detected three genes previously associated with 1,4-dioxane. The predicted functional gene analysis suggested the importance of propane monooxygenases associated with Solirubrobacter and Pseudonocardia. Overall, more microorganisms were involved in carbon uptake from 1,4-dioxane in both the wetland and agricultural soil microcosms compared to the impacted site sediment microcosms. Many of these microorganisms have not previously been associated with 1,4-dioxane removal.

Comparative Study of PtM (M=Cu, Zn, Ga, Mn, Fe, In, Ce) Bimetals on Zincosilicate for Propane Dehydrogenation Reaction.

Silicoaluminate zeolites have relatively strong Brönsted (B) acid properties that can easily lead to deep cracking reactions, making them less favourable as carriers for propane dehydrogenation. Here, we utilise zincosilicate zeolite with less B-acid produced by the introduction of the heteroatom Zn into the framework as a carrier, followed by simultaneous ion exchange (IE) of M monometallic or PtM bimetallic (M = Cu, Zn and Ga, etc.). The optimized PtZn/Zn-4 exhibits a superior propane dehydrogenation performance over PtCu/Zn-4 and PtGa/Zn-4, which can achieve a propane conversion of about 30% in a pure propane atmosphere at 550 °C and can be operated for at least 168 h without significant deactivation. Characterization techniques such as spherical aberration corrected transmission electron microscopy, in situ X-ray photoelectron spectroscopy, and in situ diffuse reflectance infrared fourier transform spectroscopy with different gas adsorptions are used to investigate these PtM@zeolite catalysts in order to deepen the understanding of acid site identification, promoter effect and catalysis.

A Smart Design of Non-noble Catalysts for Sustainable Propane Dehydrogenation.

Propane dehydrogenation (PDH), an important process for propylene synthesis, relies on expensive noble metals or highly toxic oxides as catalysts. In a recent publication in Science, Gong and coworkers report a breakthrough discovery for PDH by introducing a sustainable catalyst composed of titanium oxide overlayers encapsulating nickel nanoparticles, termed Ni@TiOx. This innovative catalyst showcases exceptional performance in PDH, exhibiting high propylene selectivity and stability under industrially relevant conditions. The study elucidates the role of defective TiOx overlayers and the electronic promotional effect of subsurface Ni in enhancing catalytic activity, translating a traditional model catalyst system into a sustainable industrial catalyst for low-carbon energy and the chemical industry.

Crystal structure of propane-1,3-diaminium squarate dihydrate.

Propane-1,3-diaminium squarate dihydrate, C3H12N2 2+·C4O4 2-·2H2O, results from the proton-transfer reaction of propane-1,3-di-amine with squaric acid and subsequent crystallization from aqueous medium. The title compound crystallizes in the tetra-gonal crystal system (space group P4bm) with Z = 2. The squarate dianion belongs to the point group D 4h and contains a crystallographic fourfold axis. The propane-1,3-diaminium dication exhibits a C 2v -symmetric all-anti conformation and resides on a special position with mm2 site symmetry. The orientation of the propane-1,3-diaminium ions makes the crystal structure polar in the c-axis direction. The solid-state supra-molecular structure features a triperiodic network of strong hydrogen bonds of the N-H⋯O and O-H⋯O types.

Highly Stable Propane Dehydrogenation on a Self-supporting Single-component Zn2SiO4 Catalyst.

Current industrial propane dehydrogenation (PDH) processes predominantly use either toxic Cr-based or expensive Pt-based catalysts, necessitating urgent exploration for alternatives. Herein, we present Zn2SiO4, an easily prepared, cost-effective material, as a highly efficient and stable catalyst for PDH. Uniquely, Zn2SiO4 nanocrystals do not require dispersion on support materials, commonly needed for catalytic active oxide clusters, but function as a self-supporting catalyst instead. During the reaction's induction period, surface Zn species on the Zn2SiO4 crystal reduce to coordinately unsaturated ZnOx single sites, serving as highly active catalytic centers. The Zn2SiO4 catalyst demonstrates a stable performance over 200 hours of PDH operation at 550 °C. We further find that introducing a minuscule amount of CO2 into the propane feed significantly extends the catalyst lifespan to over 2000 hours. This enhancement arises from the special role of CO2 in facilitating the removal of strongly adsorbed H*, preventing the complete reduction of ZnOx. After prolonged reaction, the activity of Zn2SiO4 can be fully restored by etching the surface layer to expose fresh Zn species, available throughout the crystals. The combination of CO2 introduction and catalytic site regeneration strategies is expected to enable a year-long PDH operation using a single batch of Zn2SiO4 catalyst.

Assessing personal PM2.5 exposure using a novel neck-mounted monitoring device in rural Rwanda.

There is growing global concern regarding the detrimental health impacts of PM2.5 emissions from traditional stoves that utilize polluting fuels. Conventional methods for estimating daily personal PM2.5 exposure involve personal air samplers and measuring devices placed in a waist pouch, but these instruments are cumbersome and inconvenient. To address this issue, we developed a novel neck-mounted PM2.5 monitoring device (Pocket PM2.5 Logger) that is compact, lightweight, and can operate continuously for 1 week without recharging. Twelve participants who utilized charcoal, firewood, or propane gas for cooking in rural regions of Rwanda wore the Pocket PM2.5 Logger continuously for 1 week, and time-series variations in personal PM2.5 exposure were recorded at 5-min intervals. Individual daily exposure concentrations during cooking differed significantly among users of the different fuel types, and PM2.5 exposure was at least 2.6 and 3.4 times higher for charcoal and firewood users, respectively, than for propane gas users. Therefore, switching from biomass fuels to propane gas would reduce daily individual exposure by at least one-third. An analysis of cooking times showed that the median cooking time per meal was 30 min; however, half the participants cooked for 1.5 h per meal, and one-third cooked for over 4.5 h per meal. Reducing these extremely long cooking times would reduce exposure with all fuel types. The Pocket PM2.5 Logger facilitates the comprehensive assessment of personal PM2.5 exposure dynamics and is beneficial for the development of intervention strategies targeting household air pollution.

Propane Dehydrogenation on PtxZny Active Sites in Silicalite-1.

The improvement of Pt-based catalysts for propane dehydrogenation (PDH) has progressed by recent investigations that have identified Zn as a promising promoter for Pt subnanometer catalysts. It is desirable to gain insights into the structure, stability, and activity of such active sites and the factors that influence them, such as Zn:Pt ratio, Pt coordination and nuclearity. Here, we employ density functional theory and microkinetic simulations to investigate the stability of PtxZny (x=1-3, y=0-3) active sites grafted on silanols of Silicalite-1 and the PDH activity of Pt. We find that the coordination of a Pt atom to a nest of grafted Zn(II) atoms increases the stability of the Pt1Zny sites, whose activity is similar for y=0-2 and drops dramatically for y>2. We further demonstrate, via linear scaling relations and microkinetic simulations, that the turnover frequency obeys a volcano law as a function of propylene binding strength. The Pt2Zn1 and Pt3Zn1 sites are stable and exhibit activity similar to Pt1Zn2, but only Pt1Zn2 manifests reaction kinetics consistent with experimental data, strongly suggesting the active site composition in the synthesized catalyst samples. The methodology presented here suggests a general strategy for deducing active site information such as composition through simple kinetic experiments.

Synergistic tuning of microstructure and morphology in carbon molecular sieve hollow fibers for propylene/propane separation.

Asymmetric carbon molecular sieve (CMS) hollow fiber membranes with tunable micro- and macro-structural morphologies for energy efficient propylene-propane separation are reported here.  A sub-glass transition temperature (sub-Tg) thermal oxidative crosslinking strategy enables simultaneous optimization of the intrinsic molecular sieving properties while also reducing the thickness of the CMS "skin" derived from the 6FDA:BPDA/DAM polyimide precursors. Such synergistic tuning of CMS microstructure and macroscopic morphology of CMS hollow fibers enables significantly increased propylene permeance (reaching 186.5 GPU) while maintaining an appealing propylene/propane selectivity of 13.3 for 50/50 propylene/propane mixed gas feeds. Our findings reveal a more refined and versatile tool than available with previous O2-doping pretreatments. The advanced approach here should be broadly useful to other polyimide precursors and diverse gas pairs.

Enhanced Propylene/Propane Separation via Aniline-Decorated ZIF-8 Membrane: Lattice Rigidity Adjustment and Adsorption Site Introduction.

Metal-organic framework (MOF)-based membranes excel in molecular separation, attracting significant research interest. The crystallographic microstructure and selective adsorption capacity of MOFs closely correlate with their gas separation performance. Here, aniline was added to the ZIF-8 synthesis in varying concentrations. Aniline, encapsulated within ZIF-8 cavities, interacts strongly with the 2-methylimidazole linker, resulting in both a shift in crystallographic phase from I_43m to Cm in Rietveld refinement of X-ray diffraction (XRD) patterns and the selective adsorption behavior between propylene and propane. Consequently, an aniline decorative ZIF-8 (Anix-ZIF-8) membrane was prepared using a fast current-driven synthesis method, which exhibits good propylene/propane separation selectivity of up to 85. Calculation of the interaction energy between aniline and the various crystallographic phases of ZIF-8 using density functional theory (DFT) further verifies that aniline not only promotes the formation of crystallographic Cm phase, but also enhances the adsorption selectivity of propylene over propane. Aniline modification effectively tunes the crystallographic microstructure of ZIF-8, thereby, improving molecular sieving capabilities.

Improving the Selectivity and Stability of Supported Cobalt Catalysts via Static Bi-Doping and Dynamic Trace CO2 Co-feeding during Propane Dehydrogenation.

Simultaneously enhancing selectivity and stability on supported propane dehydrogenation (PDH) catalysts remains a formidable challenge. Here, we report a combined static and dynamic strategy to address these issues synergistically. Firstly, we demonstrate a feasible sol-gel method for preparing atomically-dispersed Bi-decorated metal nanoparticle catalysts (MBi/Al2O3, M= Fe, Co, Ni, and Zn). In PDH testing, the total selectivity of by-products (CH4 and C2H6) significantly decreases to 4% for CoBi catalysts due to the static Bi-doping, compared with 16% for Co-supported catalysts. Secondly, to enhance catalytic stability, we introduce a dynamic trace CO2 co-feeding route. 10CoBi/Al2O3 catalysts exhibit superior durability against coke formation for 330 hours in PDH under a 40% C3H8 atmosphere followed by pure C3H8 conditions at 600 °C while maintaining propylene selectivity at 96%. Notably, introducing trace CO2 leads to a remarkable 6-fold decrease in the deactivation rate constant (kd). Multiple characterizations and density functional theory calculations reveal that charge transfer from atomically-distributed Bi to Co nanoparticles benefits lowering the energy of C3H6 adsorption thereby suppressing by-products. Furthermore, the dynamic co-feeding of trace CO2 facilitates coke removal, suppressing catalyst deactivation. The static Bi-doping and dynamic trace CO2 co-feeding strategy contributes simultaneously to increased selectivity and stability on supported PDH catalysts.

Characterization of cooked off-flavor volatile sulfur-containing compounds in green tea and their thermal inhibition via (-)-epigallocatechin gallate.

Cooked note is an undesired flavor in green tea, while the key odorants and inhibition mechanisms were unknown. Here, volatiles of four green tea samples and two thermal reaction models of methionine-glucose and methional were assessed using gas chromatography­sulfur chemiluminescence detector and two dimensional gas chromatography-time-of-flight mass spectrometry. Nonvolatiles of reaction models were determined using ultra performance liquid chromatography-Q-Exactive orbitrap mass spectrometry. Four cooked smelling sulfur-containing odorants including dimethyl trisulfide, dimethyl sulfide, diethyl disulfide, and methanethiol having odor activity values > 1 were characterized in tea samples. Aroma addition tests confirmed dimethyl trisulfide (> 0.4 µg/L) as a reliable predictor of the cooked note. Seven sulfur-containing odorants were detected in reaction models. The addition of (-)-epigallocatechin gallate depleted glucose and interrupted the reaction, thus reduced sulfur-containing odorants' amounts. The study provides a novel insight on targeted strategic guidance for mitigating cooked off-flavor during the thermal processing of green tea production.

Photothermal oxidative dehydrogenation of propane to propylene over Cu/BN catalysts.

Oxidative dehydrogenation of propane (ODHP) is a reaction with significant practical significance. As for the industrial application of ODHP, it is challenging to achieve high activity and high propylene selectivity simultaneously. In this study, to overcome this obstacle, we designed a series of Cu/BN catalysts with unique morphologies for establishing a photothermal ODHP system with high efficiency and selectivity. Characterization and evaluation results revealed that Cu/BN-NS and Cu/BN-NF with enlarged specific surface areas exhibited higher catalytic activities. The localized surface plasmon resonance (LSPR) effect of Cu nanoparticles further enhanced the photothermal catalytic performances of Cu/BN catalysts under visible light irradiation. To the best of our knowledge, it is the first time to establish a BN-based photothermal ODHP catalytic system. This study is expected to pave pathways to realize high activity and propylene selectivity for the practical application of ODHP.

Dynamics of direct hydrocarbon PEM fuel cells.

Hydrocarbon fuels contain approximately 50 times more energy per unit mass than commercial batteries, thus converting even 10% of the energy contained in hydrocarbon fuels to electrical energy could present a more mass-efficient electrical energy source than batteries. Considering the storability of hydrocarbon fuels compared to hydrogen, the viability of direct hydrocarbon polymer electrolyte membrane fuel cells was examined. With extremely pure (> 99.99%) propane, the cell Open-Circuit Voltage (OCV) was only 0.05 V and produced negligible power. However, with addition of trace quantities of unsaturated hydrocarbons, the cell had an OCV of 0.85 V and produced power, even after the unsaturated hydrocarbon addition was discontinued. At sufficiently high current densities, power output gradually decreased then the cell rapidly "extinguished" but by periodically shutting off the current for short time intervals the average power density could be increased significantly. Chemical analysis revealed that no significant amounts of hydrocarbon intermediates or CO were present in the effluent and that conversion of the hydrocarbon fuel to CO2 and H2O was nearly complete. An analytical model incorporating the relative rates of conversion of active anode catalyst sites to inactive sites and vice versa was developed to interpret this behavior. The model predictions were consistent with the experimental observations; possible physical mechanisms are discussed.

Highly Stable Subnanometric PtIn Clusters for the Selective Dehydrogenation of Alkanes.

Subnanometric PtIn clusters have been synthesized within pure silica MFI zeolites by post-synthetic incorporation of In to Pt@K-MFI. The optimized PtIn@K-MFI catalyst outcompetes state-of-the-art PtSn formulations in ethane and propane dehydrogenations, avoiding the need of large excess of Pt promoters and harsh reductive conditions.

Proton-Coupled Electron Transfer on Cu2O/Ti3C2Tx MXene for Propane (C3H8) Synthesis from Electrochemical CO2 Reduction.

Electrochemical CO2 reduction reaction (CO2RR) to produce value-added multi-carbon chemicals has been an appealing approach to achieving environmentally friendly carbon neutrality in recent years. Despite extensive research focusing on the use of CO2 to produce high-value chemicals like high-energy-density hydrocarbons, there have been few reports on the production of propane (C3H8), which requires carbon chain elongation and protonation. A rationally designed 0D/2D hybrid Cu2O anchored-Ti3C2Tx MXene catalyst (Cu2O/MXene) is demonstrated with efficient CO2RR activity in an aqueous electrolyte to produce C3H8. As a result, a significantly high Faradaic efficiency (FE) of 3.3% is achieved for the synthesis of C3H8 via the CO2RR with Cu2O/MXene, which is ≈26 times higher than that of Cu/MXene prepared by the same hydrothermal process without NH4OH solution. Based on in-situ attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) and density functional theory (DFT) calculations, it is proposed that the significant electrocatalytic conversion originated from the synergistic behavior of the Cu2O nanoparticles, which bound the *C2 intermediates, and the MXene that bound the *CO coupling to the C3 intermediate. The results disclose that the rationally designed MXene-based hybrid catalyst facilitates multi-carbon coupling as well as protonation, thereby manipulating the CO2RR pathway.

Simultaneous measurement of methane, propane and isobutane using a compact mid-infrared photoacoustic spectrophone.

Hydrocarbon gas sensing is a challenging task using laser absorption spectroscopy due to the complex and broad structure of absorption lines. This application requires quick, accurate and highly sensitive detection of hydrocarbon gases concentrations. In this paper, a compact photoacoustic spectrophone was developed to simultaneously measure methane, propane and isobutane. This spectrophone uses wavelength modulation spectroscopy (WMS) with a single acoustic resonator and a single DFB laser emitting at 3368 nm, which greatly reduces the system complexity without using time-division multiplexing technology for multi-gas sensing. Due to the complex and broadband absorption of hydrocarbon gases, a novel signal processing method based on multilinear regression with Ridge regression (MLR-RG) is proposed to reduce the measurement error caused by the nonlinearity of spectra signal. For single gas measurement, the detection limits of methane, propane, and isobutane are determined to be 828 ppb, 419 ppb, and 619 ppb (SNR = 1, integration time = 20 s), respectively. For simultaneous multi-gas sensing in a gaseous mixture, the detection limits of propane and isobutane are determined to be 7 ppb, 68 ppb with an integration time of 860 s, 460 s, respectively. The measurement accuracy of propane and isobutane using MLR-RG is higher than that of ordinary least squares regression and partial least squares regression by 75% and 60%, respectively. The proposed algorithm based on MLR-RG provides a promising approach to process the broad overlapping absorption spectra for accurately retrieving hydrocarbon gases concentrations.

Evolution of the Active Phase of Pt/Sn-Al2O3 Catalysts During Acidic Impregnation and Their Use in Propane Dehydrogenation.

Alumina-supported PtSn is an industrialized catalyst for propane dehydrogenation. During the catalyst impregnation, the acidic impregnation solution with chloroplatinic acid as a precursor inevitably leads to the partial dissolution of the surface of amphoteric alumina support and finally varies catalytic performance. Herein, the structure evolution of the active phase, induced by an impregnated acidic solution, was studied with special care. According to the diffused double layer theory, we proposed a model of microgels during impregnation. The microgels formed in the solution with suitable acidity on the surface of the catalysts evolved into a structure of Al2O3-coated oxidized Pt by reprecipitation during drying and calcination. The covered Pt species could be exposed by Ar+ sputtering or migrate to the surface during reduction to serve as active sites for propane dehydrogenation. Noticeably, the surface Sn0 species was generated when the pH of the impregnated solution was around 0.56, which is solid proof for the unique active phase with the PtSn alloy present on SnOx species existing on the surface of the Sn-Al2O3 support. The synthesized catalyst exhibited high propylene selectivity (99.4%) and superior stability (kd = 0.002 h-1). This study provides new insight for the precise preparation of Pt/Sn-Al2O3 catalysts.

Acid-activated α-MnO2 for photothermal co-catalytic oxidative degradation of propane: Activity and reaction mechanism.

In order to further reduce the energy consumption of the conventional thermal catalytic oxidation system and improve the degradation efficiency of pollutants, photothermal synergistic catalytic oxidation (PTSCO) system was constructed in this paper with propane as simulated pollutant representing VOCs, and then the modified α-MnO2 catalysts were prepared by using the acid activation method, which were used for the catalytic oxidation of propane in PTSCO. The α-MnO2 with appropriate acid concentration possessed excellent low-temperature reducibility, abundant active oxygen species, fast oxygen migration rate and a large number of acid sites. The optimal catalyst, H0.05-MnO2, had a T90 of 204 °C in the PTSCO system, which reduced by more than 30 °C relative to the α-MnO2 (T90 of 235 °C). Moreover, H0.05-MnO2 demonstrated excellent water resistance and long-term stability (T = 45 h). It was shown that the combination of photocatalysis and thermocatalysis can improve propane degradation by examining the kinetics of propane degradation in the PTSCO system and the conformational relationship of propane degradation by catalysts. Furthermore, a multi-pathway synergistic mechanism between photocatalysis and thermocatalysis in the PTSCO system was proposed. This work provided a theoretical basis for the preparation of high-performance catalysts and the catalytic degradation of propane.

Non-Classical Deactivation Mechanism in a Supported Intermetallic Catalyst for Propane Dehydrogenation.

Platinum-based supported intermetallic alloys (IMAs) demonstrate exceptional performance in catalytic propane dehydrogenation (PDH) primarily because of their remarkable resistance to coke formation. However, these IMAs still encounter a significant hurdle in the form of catalyst deactivation. Understanding the complex deactivation mechanism of supported IMAs, which goes beyond conventional coke deposition, requires meticulous microscopic structural elucidation. In this study, we unravel a nonclassical deactivation mechanism over a PtZn/γ-Al2O3 PDH catalyst, dictated by the PtZn to Pt3Zn nanophase transformation accompanied with dezincification. The physical origin lies in the metal support interaction (MSI) that enables strong chemical bonding between hydroxyl groups on the support and Zn sites on the PtZn phase to selectively remove Zn species followed by the reconstruction towards Pt3Zn phase. Building on these insights, we have devised a solution to circumvent the deactivation by passivating the MSI through surface modification of γ-Al2O3 support. By exchanging protons of hydroxyl groups with potassium ions (K) on the γ-Al2O3 support, such a strategy significantly minimizes the dezincification of PtZn IMA via diminished metal-support bonding, which dramatically reduces the deactivation rate from 0.2044 to 0.0587 h-1. These findings decode the nonclassical PDH deactivation mechanism over supported IMA catalysts and elaborate a new logic for the design of high-performance IMA based PDH catalysts with long-term stability.