Engineered Nanoporous Frameworks for Adsorption Cooling Applications.

The energy demand for traditional vapor-compressed technology for space cooling continues to soar year after year due to global warming and the increasing human population's need to improve living and working conditions. Thus, there is a growing demand for eco-friendly technologies that use sustainable or waste energy resources. This review discusses the properties of various refrigerants used for adsorption cooling applications followed by a brief discussion on the thermodynamic cycle. Next, sorbents traditionally used for cooling are reviewed to emphasize the need for advanced capture materials with superior properties to improve refrigerant sorption. The remainder of the review focus on studies using engineered nanoporous frameworks (ENFs) with various refrigerants for adsorption cooling applications. The effects of the various factors that play a role in ENF-refrigerant pair selection, including pore structure/dimension/shape, morphology, open-metal sites, pore chemistry and possible presence of defects, are reviewed. Next, in-depth insights into the sorbent-refrigerant interaction, and pore filling mechanism gained through a combination of characterization techniques and computational modeling are discussed. Finally, we outline the challenges and opportunities related to using ENFs for adsorption cooling applications and provide our views on the future of this technology.

Molecular-level insight into the chlorofluorocarbons adsorption by defective covalent organic polymers.

Halocarbons have important industrial applications, however they contribute to global warming and the fact that they can cause ozone depletion. Hence, the techniques that can capture and recover the used halocarbons with energy efficiency methods have recently received greater attention. In this contribution, we report the capture of dichlorodifluoromethane (R12), which has high global warming and ozone depletion potential, using covalent organic polymers (COPs). The defect-engineered COPs were synthesized and demonstrated outstanding sorption capacities, ~226 wt% of R12 combined with linear-shaped adsorption isotherms. We further identified the plausible microscopic adsorption mechanism of the investigated COPs via grand canonical Monte Carlo simulations applied to non-defective and a collection of atomistic models of the defective COPs. The modeling work suggests that significant R12 adsorption is attributed to a gradual increment of porosities due to isolated/interconnected micro-/meso-pore channels and the change of the long-range ordering of both COPs. The successive hierarchical-pore-filling mechanism promotes R12 molecular adsorption via moderate van der Waals adsorbate-adsorbent interactions in the micropores of both COPs at low pressure followed by adsorbate-adsorbate interactions in the extra-voids created at moderate to high pressure ranges. This continuous pore-filling mechanism makes defective COPs as promising sorbents for halocarbon adsorption.

Polymer Waste Valorization into Advanced Carbon Nanomaterials for Potential Energy and Environment Applications.

The rise in universal population and accompanying demands have directed toward an exponential surge in the generation of polymeric waste. The estimate predicts that world-wide plastic production will rise to ≈590 million metric tons by 2050, whereas 5000 million more tires will be routinely abandoned by 2030. Handling this waste and its detrimental consequences on the Earth's ecosystem and human health presents a significant challenge. Converting the wastes into carbon-based functional materials viz. activated carbon, graphene, and nanotubes is considered the most scientific and adaptable method. Herein, this world provides an overview of the various sources of polymeric wastes, modes of build-up, impact on the environment, and management approaches. Update on advances and novel modifications made in methodologies for converting diverse types of polymeric wastes into carbon nanomaterials over the last 5 years are given. A remarkable focus is made to comprehend the applications of polymeric waste-derived carbon nanomaterials (PWDCNMs) in the CO2 capture, removal of heavy metal ions, supercapacitor-based energy storage and water splitting with an emphasis on the correlation between PWDCNMs' properties and their performances. This review offers insights into emerging developments in the upcycling of polymeric wastes and their applications in environment and energy.

Manipulating Pore Topology and Functionality to Promote Fluorocarbon-Based Adsorption Cooling.

ConspectusWith the worldwide demand for refrigeration and cooling expected to triple, it is increasingly important to search for alternative energy resources to drive refrigeration cycles with reduced electricity consumption. Recently, adsorption cooling has gained increased attention since energy reallocation in such systems is based on gas adsorption/desorption, which can be driven by waste/natural heat sources. Eco-friendly sorption-based cooling relies on the cyclic transfer of refrigerant gas from a high to low energy state by the pseudocompression effect resulting from adsorption and desorption. The driving force for energy transfer relies on heat rather than electricity. The performance of a sorption chiller is primarily influenced by this cyclic sorption behavior, which is characterized as the working capacity of the porous sorbent. Thus, increases in this working capacity directly translate to a more compact and efficient cooling system. However, a lack of highly effective sorbent/refrigerant pairs lowers cooling performance and therefore has limited applicability. To this end, synthetic metal-organic frameworks (MOFs) and covalent organic polymers (COPs) possess higher porosity and greater tunability leading to more substantial potential benefits for adsorption, compared to traditional sorbent materials. Similarly, hydrofluorocarbon refrigerants have more favorable applicability given the ease of operation above atmospheric pressures due to suitable saturated vapor pressures and boiling points. For these reasons, our work focuses on an ongoing strategy to promote sorption cooling via improvements in the sorbent/refrigerant pair. Specifically, we target the interaction of hydrofluorocarbon refrigerants with MOF/COP materials at a molecular level by interpreting the host-guest chemistry and the role of framework pore topology. These molecular-level differences translate to cooling performance, which is described herein. These strategies include engineering framework porosity (i.e., pore size, pore volume) by using elongated organic linkers and stereochemistry control during synthesis; manipulating the sorbate/sorbent interaction by introducing functional moieties or unsaturated metal centers to enhance working capacities in narrow pressure ranges; varying pore topology/morphology to impact adsorption isotherm behavior; and leveraging defective sites within the frameworks to further enhance adsorption capability. This atomic level understanding of sorbate-sorbent interactions is conducted using various in situ experimental techniques such as synchrotron-based X-ray diffraction, X-ray absorption spectroscopy, in situ Fourier transform infrared spectroscopy, and direct sorption energies determinization with calorimetry. Moreover, the experimentally studied interactions and the corresponding adsorption mechanism are corroborated by computational studies using density functional theory (DFT) and grand canonical Monte Carlo (GCMC) simulations. Using this approach, we have made strides toward engineering designed frameworks with precise molecular control to target refrigerant molecules and thereby enhance the performance of desired working pairs for sorption-based cooling.

Porous Covalent Organic Polymers for Efficient Fluorocarbon-Based Adsorption Cooling.

Adsorption-based cooling is an energy-efficient renewable-energy technology that can be driven using low-grade industrial waste heat and/or solar heat. Here, we report the first exploration of fluorocarbon adsorption using porous covalent organic polymers (COPs) for this cooling application. High fluorocarbon R134a equilibrium capacities and unique overall linear-shaped isotherms are revealed for the materials, namely COP-2 and COP-3. The key role of mesoporous defects on this unusual adsorption behavior was demonstrated by molecular simulations based on atomistic defect-containing models built for both porous COPs. Analysis of simulated R134a adsorption isotherms for various defect-containing atomistic models of the COPs shows a direct correlation between higher fluorocarbon adsorption capacities and increasing pore volumes induced by defects. Combined with their high porosities, excellent reversibility, fast kinetics, and large operating window, these defect-containing porous COPs are promising for adsorption-based cooling applications.

Molecular Insight into Fluorocarbon Adsorption in Pore Expanded Metal-Organic Framework Analogs.

The rapid growth in the global energy demand for space cooling requires the development of more efficient environmental chillers for which adsorption-based cooling systems can be utilized. Here, in this contribution, we explore sorbents for chiller use via a pore-engineering concept to construct analogs of the 1-dimensional pore metal-organic framework MOF-74 by using elongated organic linkers and stereochemistry control. The prepared pore-engineered MOFs show remarkable equilibrium adsorption of the selected fluorocarbon refrigerant that is translated to a modeled adsorption-based refrigeration cycle. To probe molecular level interactions at the origin of these unique adsorption properties for this series of Ni-MOFs, we combined in situ synchrotron X-ray powder diffraction, neutron powder diffraction, X-ray absorption spectroscopy, calorimetry, Fourier transform infrared techniques, and molecular simulations. Our results reveal the coordination of fluorine (of CH2F in R134a) to the nickel(II) open metal centers at low pressures for each Ni-MOF analog and provide insight into the pore filling mechanism for the full range of the adsorption isotherms. The newly designed Ni-TPM demonstrates exceptional R134a adsorption uptake compared to its parent microporous Ni-MOF-74 due to larger engineered pore size/volume. The application of this adsorption performance toward established chiller conditions yields a working capacity increase for Ni-TPM of about 400% from that of Ni-MOF-74, which combined with kinetics directly correlates to both a higher coefficient of performance and a higher average cooling capacity generated in a modeled chiller.

An Ultra-Microporous Metal-Organic Framework with Exceptional Xe Capacity.

Molecular confinement plays a significant effect on trapped gas and solvent molecules. A fundamental understanding of gas adsorption within the porous confinement provides information necessary to design a material with improved selectivity. In this regard, metal-organic framework (MOF) adsorbents are ideal candidate materials to study confinement effects for weakly interacting gas molecules, such as noble gases. Among the noble gases, xenon (Xe) has practical applications in the medical, automotive and aerospace industries. In this Communication, we report an ultra-microporous nickel-isonicotinate MOF with exceptional Xe uptake and selectivity compared to all benchmark MOF and porous organic cage materials. The selectivity arises because of the near perfect fit of the atomic Xe inside the porous confinement. Notably, at low partial pressure, the Ni-MOF interacts very strongly with Xe compared to the closely related Krypton gas (Kr) and more polarizable CO2 . Further 129 Xe NMR suggests a broad isotropic chemical shift due to the reduced motion as a result of confinement.

Transition-Metal Nitroprussides Examined for Water Harvesting and Sorption Cooling.

Transition-metal pentacyanonitrosylferrates, commonly known as nitroprussides, have a long and documented history. Here, we synthesize cobalt and nickel nitroprussides (NPs) in order to probe their use as sorbents for water and fluorocarbon uptake for potential water harvesting and cooling applications. These NPs show stable and reversible equilibrium sorption isotherms at room temperature with peak uptake values of ∼40 wt % for H2O and ∼30 wt % for fluorocarbon R134a. At water harvesting conditions, working capacities of ∼19 wt % were obtained for NPs. At sorption cooling conditions, the working capacities favored nickel NP. Given the advantages of an easy, inexpensive, and scalable synthesis, this study demonstrates the potential for using nitroprussides for future water harvesting and adsorption cooling systems.

Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal-Organic Framework.

Mononuclear and dinuclear copper species were synthesized at the nodes of an NU-1000 metal-organic framework (MOF) via cation exchange and subsequent oxidation at 200 °C in oxygen. Copper-exchanged MOFs are active for selectively converting methane to methanol at 150-200 °C. At 150 °C and 1 bar methane, approximately a third of the copper centers are involved in converting methane to methanol. Methanol productivity increased by 3-4-fold and selectivity increased from 70% to 90% by increasing the methane pressure from 1 to 40 bar. Density functional theory showed that reaction pathways on various copper sites are able to convert methane to methanol, the copper oxyl sites with much lower free energies of activation. Combining studies of the stoichiometric activity with characterization by in situ X-ray absorption spectroscopy and density functional theory, we conclude that dehydrated dinuclear copper oxyl sites formed after activation at 200 °C are responsible for the activity.

Isoreticular Expansion of Metal-Organic Frameworks via Pillaring of Metal Templated Tunable Building Layers: Hydrogen Storage and Selective CO2 Capture.

The deliberate construction of isoreticular eea-metal-organic frameworks (MOFs) (Cu-eea-1, Cu-eea-2 and Cu-eea-3) and rtl-MOFs (Co-rtl-1 and Co-rtl-2) has been accomplished based on the ligand-to-axial pillaring of supermolecular building layers. The use of different metal ions resulted in two types of supermolecular building layers (SBLs): Kagome (kgm) and square lattices (sql) which further interconnect to form anticipated 3D-MOFs. The isoreticular expansion of (3,6)-connected Cu-MOFs has been achieved with desired eea-topology based on kgm building layers. In addition, two (3,6)-connected Co-rtl-MOFs were also successfully constructed based on sql building layers. The Cu-eea-MOFs were shown to act as hydrogen storage materials with appreciable amount of hydrogen uptake abilities. Moreover Cu-eea-MOFs have also exhibited remarkable CO2 capture ability at ambient condition compared to nitrogen and methane, due to the presence of amide functionalities.

Probing the Sorption of Perfluorooctanesulfonate Using Mesoporous Metal-Organic Frameworks from Aqueous Solutions.

One approach to reduce increasing concentrations of toxic per- and polyfluoroalkyl substances (PFAS) involves the capture of PFAS from aqueous media using porous materials. The use of highly porous, tunable metal organic framework (MOF) materials is appealing for targeted liquid phase sorption. In this work, we demonstrate the excellent capture of perfluorooctanesulfonate (PFOS) using both the chromium and iron analogs of the MIL-101 framework. Experimental characterization of PFOS uptake reveals unique differences in sorption properties between these two analogs, providing key implications for future PFOS sorbent design. Specifically, STEM-EDS and IR spectroscopy show definitive proof of sorption. Furthermore, XPS analysis shows evidence of a strong interaction between sulfur atoms of the polar headgroup of PFOS and the metal center of the framework in addition to the fluorinated nonpolar tail. Additionally, in situ 19F NMR reveals higher PFOS affinity for Cr-MIL-101 versus Fe-MIL-101 based on sorption kinetics. Surprisingly, at these relatively high PFOS concentrations, activated acetylene black carbon is severely outperformed by both MOFs.

Pore-Engineered Metal-Organic Frameworks with Excellent Adsorption of Water and Fluorocarbon Refrigerant for Cooling Applications.

Metal-organic frameworks (MOFs) have shown promising behavior for adsorption cooling applications. Using organic ligands with 1, 2, and 3 phenylene rings, we construct moisture-stable Ni-MOF-74 members with adjustable pore apertures, which exhibit excellent sorption capabilities toward water and fluorocarbon R134a. To our knowledge, this is the first report of adsorption isotherms of fluorocarbon R134a in MOFs. The adsorption patterns for these materials differ significantly and are attributed to variances in their hydrophobic/hydrophilic pore character associated with differences in pore size.

Synthesis Strategies for Ultrastable Zeolite GIS Polymorphs as Sorbents for Selective Separations.

Designing zeolites with tunable physicochemical properties can substantially impact their performance in commercial applications, such as adsorption, separations, catalysis, and drug delivery. Zeolite synthesis typically requires an organic structure-directing agent to produce crystals with specific pore topology. Attempts to remove organics from syntheses to achieve commercially viable methods of preparing zeolites often lead to the formation of impurities. Herein, we present organic-free syntheses of two polymorphs of the small-pore zeolite P (GIS), P1 and P2. Using a combination of adsorption measurements and density functional theory calculations, we show that GIS polymorphs are selective adsorbents for H2 O relative to other light gases (e.g., H2 , N2 , CO2 ). Our findings refute prior theoretical studies postulating that GIS-type zeolites are excellent materials for CO2 separation/sequestration. We also show that P2 is significantly more thermally stable than P1, which broadens the operating conditions for GIS-type zeolites in commercial applications and opens new avenues for exploring their potential use in processes such as catalysis.

Hierarchical Porous Activated Carbon from Wheat Bran Agro-Waste: Applications in Carbon Dioxide Capture, Dye Removal, Oxygen and Hydrogen Evolution Reactions.

This work reports an efficient method for facile synthesis of hierarchically porous carbon (WB-AC) utilizing wheat bran waste. Obtained carbon showed 2.47 mmol g-1 CO2 capture capacity with good CO2 /N2 selectivity and 27.35 to 29.90 kJ mol-1 isosteric heat of adsorption. Rapid removal of MO dye was observed with a capacity of ~555 mg g-1 . Moreover, WB-AC demonstrated a good OER activity with 0.35 V low overpotential at 5 mA cm-2 and a Tafel slope of 115 mV dec-1 . It also exhibited high electrocatalytic HER activity with 57 mV overpotential at 10 mA cm-2 and a Tafel slope of 82.6 mV dec-1 . The large SSA (757 m2 g-1 ) and total pore volume (0.3696 cm3 g-1 ) result from N2 activation contributing to selective CO2 uptake, high and rapid dye removal capacity and superior electrochemical activity (OER/HER), suggesting the use of WB-AC as cost effective adsorbent and metal free electrocatalyst.

Understanding formation thermodynamics of structurally diverse zeolite oligomers with first principles calculations.

The mechanisms of many zeolitic processes, including nucleation and interzeolite transformation, are not fully understood owing to complex growth mixtures that obfuscate in situ monitoring of molecular events. In this work, we provide insights into zeolite chemistry by investigating the formation thermodynamics of small zeolitic species using first principles calculations. We systematically study how formation energies of pure-silicate and aluminosilicate species differ by structure type and size, temperature, and the presence of alkali or alkaline earth metal cations (Na+, K+, and Ca2+). Highly condensed (cage-like) species are found to be strongly preferred to simple rings in the pure-silicate system, and this thermodynamic preference increases with temperature. Introducing aluminum leads to more favorable formation thermodynamics for all species. Moreover, for species with a low Si/Al ratio (≤2), a thermodynamic preference does not exist among structure types; instead, a pool of diverse aluminosilicate structures compete in formation. Metal cation effects strongly depend on the presence of aluminum, cage size, cation type, and location, since each of these factors can alter electrostatic interactions between cations and zeolitic species. We reveal that confined metal cations may destabilize pure-silicate cages due to localized interactions; conversely, they stabilize aluminosilicates due to strong cation-framework attractions in sufficiently large cages. Importantly, this work rationalizes a series of experimental observations and can potentially guide efforts for controlling zeolite nucleation/crystallization processes.

Enhanced Iodine Capture Using a Postsynthetically Modified Thione-Silver Zeolitic Imidazole Framework.

Efficient management of radionuclides that are released from various processes in the nuclear fuel cycle is of significant importance. Among these nuclides, radioactive iodine (mainly 129I and 131I) is a major concern due to the risk it poses to the environment and to human health; thus, the development of materials that can capture and safely store radioactive iodine is crucial. Herein, a novel silver-thione-functionalized zeolitic imidazole framework (ZIF) was synthesized via postsynthetic modification and assessed for its iodine uptake capabilities alongside the parent ZIF-8 and intermediate materials. A solvent-assisted ligand exchange procedure was used to replace the 2-methylimidazole linkers in ZIF-8 with 2-mercaptoimidazole, forming intermediate compound ZIF-8 = S, which was reacted with AgNO3 to yield the ZIF-8 = S-Ag+ composite for iodine uptake. Despite possessing the lowest BET surface area of the derivatives, the Ag-functionalized material demonstrated superior I2 adsorption in terms of both maximum capacity (550 g I2/mol) and rapid kinetics (50% loading achieved in 5 h, saturation in 50 h) compared to that of our pristine ZIF-8, which reached 450 g I2/mol after 150 h and 50% loading in 25 h. This improvement is attributed to the presence of the Ag+ ions, which provide a strong chemical driving force to form a stable Ag-I species. The results of this study contribute to a broader understanding of the strategies that can be employed to engineer adsorbents with robust iodine uptake behavior.

Novel catalysts with multivalence copper for organic pollutants removal from wastewater with excellent selectivity and stability in Fenton-like process under neutral pH conditions.

Fenton-like reaction has been widely used for organics degradation. However, most Fenton-like reaction works at low pH range (pH < 4) with uncontrollable selectivity of hydroxyl radicals from H2 O2 activation, and unsatisfied catalyst stability, which is compromised advanced oxidation performance for water/wastewater treatments. In this work, to solve the drawbacks, novel copper catalysts were fabricated via hydrogen reduction/calcination of Cu2+ -supported Al/MCM-41 with precisely controllable copper valence state. Compared with catalysts with monovalence copper (i.e., CuO, Cu, and Cu2+ ), the obtained catalysts with multivalence copper present higher selectivity, excellent stability towards •OH radical pathways, and outperformance in pCBA degradation efficiency at neutral state. In addition, the fabricated catalysts also exhibited excellent phenol removal efficiency (75.5%) and H2 O2 utilization efficiency (47.9%) within neutral environment. Moreover, the degradation efficiency of phenol approaches to 100% within only 2 h. The catalyst also shows good stability for organic pollutants removal, which shows good potential in catalytic oxidation for phenolic compounds-containing wastewater in Fenton-like reaction, especially under neutral pH conditions. PRACTITIONER POINTS: Multivalence copper presents great potentials for organic compounds removal at neutral condition. Multivalence copper shows higher selectivity toward •OH and good stability at neutral condition. Multivalence copper exhibiters outperformed phenol removal efficiency at neutral condition.

Role of Zeolite Structural Properties toward Iodine Capture: A Head-to-head Evaluation of Framework Type and Chemical Composition.

This study evaluated zeolite-based sorbents for iodine gas [I2(g)] capture. Based on the framework structures and porosities, five zeolites, including two faujasite (FAU), one ZSM-5 (MFI), one mesoMFI, one ZSM-22 (TON), as well as two mesoporous materials, were evaluated for I2(g) capture at room temperature and 150 °C in an iodine-saturated environment. From these preliminary studies, the three best-performing zeolites were ion-exchanged with Ag+ and evaluated for I2(g) capture under similar conditions. Energy-dispersive X-ray spectroscopy data suggest that Ag-FAU frameworks were the materials with the highest capacity for I2(g) in this study, showing ∼3× higher adsorption compared to Ag-mordenite (Ag-MOR) at room temperature, but X-ray diffraction measurements show that the faujasite structure collapsed during the adsorption studies because of dealumination. The Ag-MFI zeolites are decent sorbents in real-life applications, showing both good sorption capacities and higher stability. In-depth analyses and characterizations, including synchrotron X-ray absorption spectroscopy, revealed the influence of structural and chemical properties of zeolites on the performance for iodine adsorption from the gas phase.

Structure-Property Correlation of Hierarchically Porous Carbons for Fluorocarbon Adsorption.

Although traditional commercially available porous carbon-fluorocarbon working pairs have shown promising applicability for adsorption cooling, advancements in engineered carbons may further improve the performance. Moreover, insights into structure-property relationships that target higher sorption capacities within these synthesized carbons may guide such materials' future design. We utilized hierarchically porous carbons (HPCs), synthesized with colossal microporous and mesoporous content characterized by high surface areas (up to 2689 m2/g) and pore volume values (up to 10.31 cm3/g) toward fluorocarbon R134a adsorption. This unique pore topology leads to exceptional R134a uptake, ∼250 wt %, outperforming the highest uptake carbon material to date, Maxsorb III (∼220 wt %). Material characterizations reveal that the outstanding R134a capacity may be attributed to textural properties and oxygen-terminated functional groups more than graphitization of the material. Most importantly, HPCs are efficiently utilized in a two-bed model chiller device, where the performance shows excellent working capacity (105 wt %, ∼2 times the value of reported carbon materials/R134a). Fluorocarbon adsorption on HPCs also displays fast kinetics (equilibrium time: ∼2 min) mainly driven by physical adsorption (Qst: ∼27 kJ/mol), characteristic of swiftly reversible behavior adsorption-desorption behaviors. This work provides a fundamental understanding of the applicability of HPCs/R134a working pair for adsorption cooling.

ESSENCE - A rapid, shear-enhanced, flow-through, capacitive electrochemical platform for rapid detection of biomolecules.

The rapid, sensitive, and selective detection of target analytes using electrochemical sensors is challenging. ESSENCE, a new Electrochemical Sensor that uses a Shear-Enhanced, flow-through Nanoporous Capacitive Electrode, overcomes current electrochemical sensors' response limitations, selectivity, and sensitivity limitations. ESSENCE is a microfluidic channel packed with transducer material sandwiched by a top and bottom microelectrode. The room-temperature instrument less integration process allows the switch of the transducer materials to make up the porous electrode without modifying the electrode architecture or device protocol. ESSENCE can be used to detect both biomolecules and small molecules by simply changing the packed transducer material. Electron microscopy results confirm the high porosity. In conjunction with the non-planar interdigitated electrode, the packed transducer material results in a flow-through porous electrode. Electron microscopy results confirm the high porosity. The enhanced shear forces and increased convective fluxes disrupt the electric double layer's (EDL) diffusive process in ESSENCE. This disruption migrates the EDL to high MHz frequency allowing the capture signal to be measured at around 100 kHz, significantly improving device timing (rapid detection) with a low signal-to-noise ratio. The device's unique architecture allows us multiple configuration modes for measuring the impedance signal. This allows us to use highly conductive materials like carbon nanotubes. We show that by combining single-walled carbon nanotubes as transducer material with appropriate capture probes, NP-µIDE has high selectivity and sensitivity for DNA (fM sensitivity, selective against non-target DNA), breast cancer biomarker proteins (p53, pg/L sensitivity, selective against non-target HER2).