Probing the Kinetic Origin of Varying Oxidative Stability of Ethyl- vs. Propyl-spaced Amines for Direct Air Capture.

Amine-based adsorbents are promising for direct air capture of CO2 , yet oxidative degradation remains a key unmitigated risk hindering wide-scale deployment. Borrowing wisdom from the basic auto-oxidation scheme, insights are gained into the underlying degradation mechanisms of polyamines by quantum chemical, advanced sampling simulations, adsorbent synthesis, and accelerated degradation experiments. The reaction kinetics of polyamines are contrasted with that of typical aliphatic polymers and they elucidate for the first time the critical role of aminoalkyl hydroperoxide decomposition in the oxidative degradation of amino-oligomers. The experimentally observed variation in oxidative stability of polyamines with different backbone structures is explained by the relationship between the local chemical structure and the free energy barrier of aminoalkyl hydroperoxide decomposition, suggesting that its energetics can be used as a descriptor to screen and design new polyamines with improved stability. The developed computational capability sheds light on radical-induced degradation chemistry of other organic functional materials.

Ultra-low-density digitally architected carbon with a strutted tube-in-tube structure.

Porous materials with engineered stretching-dominated lattice designs, which offer attractive mechanical properties with ultra-light weight and large surface area for wide-ranging applications, have recently achieved near-ideal linear scaling between stiffness and density. Here, rather than optimizing the microlattice topology, we explore a different approach to strengthen low-density structural materials by designing tube-in-tube beam structures. We develop a process to transform fully dense, three-dimensional printed polymeric beams into graphitic carbon hollow tube-in-tube sandwich morphologies, where, similar to grass stems, the inner and outer tubes are connected through a network of struts. Compression tests and computational modelling show that this change in beam morphology dramatically slows down the decrease in stiffness with decreasing density. In situ pillar compression experiments further demonstrate large deformation recovery after 30-50% compression and high specific damping merit index. Our strutted tube-in-tube design opens up the space and realizes highly desirable high modulus-low density and high modulus-high damping material structures.

Cellular fluidics.

The natural world provides many examples of multiphase transport and reaction processes that have been optimized by evolution. These phenomena take place at multiple length and time scales and typically include gas-liquid-solid interfaces and capillary phenomena in porous media1,2. Many biological and living systems have evolved to optimize fluidic transport. However, living things are exceptionally complex and very difficult to replicate3-5, and human-made microfluidic devices (which are typically planar and enclosed) are highly limited for multiphase process engineering6-8. Here we introduce the concept of cellular fluidics: a platform of unit-cell-based, three-dimensional structures-enabled by emerging 3D printing methods9,10-for the deterministic control of multiphase flow, transport and reaction processes. We show that flow in these structures can be 'programmed' through architected design of cell type, size and relative density. We demonstrate gas-liquid transport processes such as transpiration and absorption, using evaporative cooling and CO2 capture as examples. We design and demonstrate preferential liquid and gas transport pathways in three-dimensional cellular fluidic devices with capillary-driven and actively pumped liquid flow, and present examples of selective metallization of pre-programmed patterns. Our results show that the design and fabrication of architected cellular materials, coupled with analytical and numerical predictions of steady-state and dynamic behaviour of multiphase interfaces, provide deterministic control of fluidic transport in three dimensions. Cellular fluidics may transform the design space for spatial and temporal control of multiphase transport and reaction processes.

Unraveling the Ion Adsorption Kinetics in Microporous Carbon Electrodes: A Multiscale Quantum-Continuum Simulation and Experimental Approach.

Understanding sorption in porous carbon electrodes is crucial to many environmental and energy technologies, such as capacitive deionization (CDI), supercapacitor energy storage, and activated carbon filters. In each of these examples, a practical model that can describe ion electrosorption kinetics is highly desirable for accelerating material design. Here, we proposed a multiscale model to study the ion electrosorption kinetics in porous carbon electrodes by combining quantum mechanical simulations with continuum approaches. Our model integrates the Butler-Volmer (BV) equation for sorption kinetics and a continuously stirred tank reactor (CSTR) formulation with atomistic calculations of ion hydration and ion-pore interactions based on density functional theory (DFT). We validated our model experimentally by using ion mixtures in a flow-through electrode CDI device and developed an in-line UV absorption system to provide unprecedented resolution of individual ions in the separation process. We showed that the multiscale model captures unexpected experimental phenomena that cannot be explained by the traditional ion electrosorption theory. The proposed multiscale framework provides a viable approach for modeling separation processes in systems where pore sizes and ion hydration effects strongly influence the sorption kinetics, which can be leveraged to explore possible strategies for improving carbon-based and, more broadly, pore-based technologies.

A New Class of Molecular Electrocatalysts for Hydrogen Evolution: Catalytic Activity of M3N@C2n (2n = 68, 78, and 80) Fullerenes.

The electrocatalytic properties of some endohedral fullerenes for hydrogen evolution reactions (HER) were recently predicted by DFT calculations. Nonetheless, the experimental catalytic performance under realistic electrochemical environments of these 0D-nanomaterials have not been explored. Here, for the first time, we disclose the HER electrocatalytic behavior of seven M3N@2n (2n = 68, 78, and 80) fullerenes (Gd3N@Ih(7)-C80, Y3N@Ih(7)-C80, Lu3N@Ih(7)-C80, Sc3N@Ih(7)-C80, Sc3N@D5h(6)-C80, Sc3N@D3h(5)-C78, and Sc3N@D3(6140)-C68) using a combination of experimental and theoretical techniques. The non-IPR Sc3N@D3(6140)-C68 compound exhibited the best catalytic performance toward the generation of molecular hydrogen, exhibiting an onset potential of -38 mV vs RHE, a very high mass activity of 1.75 A·mg-1 at -0.4 V vs RHE, and an excellent electrochemical stability, retaining 96% of the initial current after 24 h. The superior performance was explained on the basis of the fused pentagon rings, which represent a new and promising HER catalytic motif.

Selectivity of nitrate and chloride ions in microporous carbons: the role of anisotropic hydration and applied potentials.

Understanding ion transport in porous carbons is critical for a wide range of technologies, including supercapacitors and capacitive deionization for water desalination, yet many details remain poorly understood. For instance, an atomistic understanding of how ion selectivity is influenced by the molecular shape of ions, morphology of the micropores and applied voltages is largely lacking. In this work, we combined molecular dynamics simulations with enhanced sampling methods to elucidate the mechanism of nitrate and chloride selectivity in subnanometer graphene slit-pores. We show that nitrate is preferentially adsorbed over chloride in the slit-like micropores. This preferential adsorption was found to stem from the weaker hydration energy and unique anisotropy of the ion solvation of nitrate. Beside the effects of ion dehydration, we found that applied potential plays an important role in determining the ion selectivity, leading to a lower selectivity of nitrate over chloride at a high applied potential. We conclude that the measured ion selectivity results from a complex interplay between voltage, confinement, and specific ion effects-including ion shape and local hydration structure.

Cation Selectivity in Capacitive Deionization: Elucidating the Role of Pore Size, Electrode Potential, and Ion Dehydration.

Capacitive deionization (CDI) is a promising water desalination technology that is applicable to the treatment of low-salinity brackish waters and the selective removal of ionic contaminants. In this work, we show that by making a small change in the synthetic procedure of hierarchical carbon aerogel monolith (HCAM) electrodes, we can adjust the pore-size distribution and tailor the selectivity, effectively switching between selective adsorption of calcium or sodium ions. Ion selectivity was measured for a mixture of 5 mM NaCl and 2.5 mM CaCl2. For the low activated flow-through CDI (fteCDI) cell, we observed extremely high sodium selectivity over calcium (SNa/Ca ≫ 10, no Ca2+ adsorbed) at all of the applied potentials, while for the highly activated fteCDI cell, we observed a selectivity value of 6.6 ± 0.8 at 0.6 V for calcium over sodium that decreased to 2.2 ± 0.03 at 1.2 V. Molecular dynamics simulations indicated that the loss in Ca2+ selectivity over Na+ at high applied voltages could be due to a competition between ion-pore electrostatic interactions and volume exclusion ("crowding") effects. Interestingly, we also find with these simulations that the relative sizes of the ions change due to changes in hydration at a higher voltage.

Three-Dimensional Printable Sodium Carbonate Composite Sorbents for Efficient Biogas Upgrading.

We have developed a new class of sodium carbonate/silicone composite sorbents that selectively capture carbon dioxide (CO2) and can purify biogas to natural gas pipeline-quality biomethane. These nontoxic composites can be three-dimensionally printed or extruded at low costs, can have high specific CO2 sorption rates (in excess of 5 µmol s-1 g-1 bar-1) and high selectivity due to their chemical mechanism, and can be regenerated with low-energy air stripping. Therefore, these composite sorbents combine the high selectivity of liquid sorbents with the high specific sorption rates and low regeneration energies found in many solid sorbents. We characterized these composite sorbents with X-ray computed tomography, scanning electron microscopy (SEM), and X-ray diffraction (XRD). Furthermore, we measured composite sorption capacities of up to 0.62 mol CO2 kg-1 and recorded breakthrough curves in a flow-through, fixed-bed reactor using both simulated biogas and locally sourced industrial biogas. Additional tests of the composite sorbent were carried out with pure CO2 in a sealed pressure drop apparatus. This experimental data was used to validate a numerical model of the setup and to simulate an industrial-scale biogas upgrading process. Finally, we performed a preliminary technoeconomic analysis for this upgrading process and found that this composite sorbent can upgrade biogas at a lower cost (∼$0.97 per GJ) than other currently implemented techniques.

Highly selective encapsulation and purification of U-based C78-EMFs within a supramolecular nanocapsule.

The ability of the tetragonal prismatic nanocapsule 1·(BArF)8 to selectively encapsulate U-based C78 EMFs from a soot mixture is reported, showing enhanced affinity for C78-based EMFs over C80-based EMFs. Molecular recognition driven by the electrostatic interactions between the host and guest is at the basis of the high selectivity observed for ellipsoidal C78-based EMFs compared to spherical C80-based EMFs. In addition, DFT analysis points towards an enhanced breathing adaptability of nanocapsule 1·(BArF)8 to C78-based EMFs to further explain the selectivity observed when the host is used in the solid phase.

Specific ion effects at graphitic interfaces.

Improved understanding of aqueous solutions at graphitic interfaces is critical for energy storage and water desalination. However, many mechanistic details remain unclear, including how interfacial structure and response are dictated by intrinsic properties of solvated ions under applied voltage. In this work, we combine hybrid first-principles/continuum simulations with electrochemical measurements to investigate adsorption of several alkali-metal cations at the interface with graphene and within graphene slit-pores. We confirm that adsorption energy increases with ionic radius, while being highly dependent on the pore size. In addition, in contrast with conventional electrochemical models, we find that interfacial charge transfer contributes non-negligibly to this interaction and can be further enhanced by confinement. We conclude that the measured interfacial capacitance trends result from a complex interplay between voltage, confinement, and specific ion effects-including ion hydration and charge transfer.

Integration of Fullerenes as Electron Acceptors in 3D Graphene Networks: Enhanced Charge Transfer and Stability through Molecular Design.

Here, we report a concept that allows the integration of the characteristic properties of [60]fullerene in 3D graphene networks. In these systems, graphene provides high electrical conductivity and surface area while fullerenes add high electron affinity. We use molecular design to optimize the interaction between 3D graphene networks and fullerenes, specifically in the context of stability and charge transfer in an electrochemical environment. We demonstrated that the capacity of the 3D graphene network is significantly improved upon the addition of C60 and C60 monoadducts by providing additional acceptor states in the form of low-lying lowest unoccupied molecular orbitals of C60 and its derivative. Guided by experimental results and first-principles calculations, we synthesized and tested a C60 monoadduct with increased stability by strengthening the 3D graphene-C60 van-der-Waals interactions. The synthesis method and stabilization strategy presented here is expected to benefit the integration of graphene-C60 hybrid materials in solar cell and charge storage applications.

Using Ultramicroporous Carbon for the Selective Removal of Nitrate with Capacitive Deionization.

The contamination of water resources with nitrate is a growing and significant problem. Here we report the use of ultramicroporous carbon as a capacitive deionization (CDI) electrode for selectively removing nitrate from an anion mixture. Through moderate activation, we achieve a micropore-size distribution consisting almost exclusively of narrow (<1 nm) pores that are well suited for adsorbing the planar, weakly hydrated nitrate molecule. Cyclic voltammetry measurements reveal an enhanced capacitance for nitrate when compared to chloride as well as significant ion sieving effects when sulfate is the only anion present. We measure high selectivities (S) of both nitrate over sulfate (SNO3/SO4 = 17.8 ± 3.6 at 0.6 V) and nitrate over chloride (SNO3/Cl = 6.1 ± 0.4 at 0.6 V) when performing a constant voltage CDI separation on 3.33 mM/3.33 mM/1.67 mM Cl/NO3/SO4 feedwater. These results are particularly encouraging considering that a divalent interferant was present in the feed. Using molecular dynamics simulations, we examine the solvation characteristics of these ions to better understand why nitrate is preferentially electrosorbed over sulfate and chloride.

Correction: A new family of fullerene derivatives: fullerene-curcumin conjugates for biological and photovoltaic applications.

[This corrects the article DOI: 10.1039/C8RA08334G.].

Origins and Implications of Interfacial Capacitance Enhancements in C60-Modified Graphene Supercapacitors.

Understanding and controlling the electrical response at a complex electrode-electrolyte interface is key to the development of next-generation supercapacitors and other electrochemical devices. In this work, we apply a theoretical framework based on the effective screening medium and reference interaction site model to explore the role of electrical double-layer (EDL) formation and its interplay with quantum capacitance in graphene-based supercapacitors. In addition to pristine graphene, we investigate a novel C60-modified graphene supercapacitor material, which promises higher charge-storage capacity. Beyond the expected enhancement in the quantum capacitance, we find that the introduction of C60 molecules significantly alters the EDL response. These changes in EDL are traced to the interplay between surface morphology and charge localization character and ultimately dominate the overall capacitive improvement in the hybrid system. Our study highlights a complex interplay among surface morphology, electronic structure, and interfacial capacitance, suggesting general improvement strategies for optimizing carbon-based supercapacitor materials.

A new family of fullerene derivatives: Fullerene-curcumin conjugates for biological and photovoltaic applications.

The synthesis and characterization of a family of [60]fullerocurcuminoids obtained via Bingel reactions is reported. The new C60 derivatives include curcumin and curcuminoids with a variety of end groups. Preliminary biological experiments show the potential activity of the compound containing a curcumin addend, which exhibits moderate anti-HIV-1 and radical scavenger properties, but no anti-cancer activity. In addition, the new fullerocurcuminoids exhibit HOMO/LUMO energy levels that are reasonably matched with those of perovskites and when they were tested in perovskite solar cells (PSCs) as the electron transporting material (ETM), photoconversion efficiencies ranging from 14.04%-14.95% were obtained, whereas a value of 16.23% was obtained for [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) based devices.

Transformation of doped graphite into cluster-encapsulated fullerene cages.

An ultimate goal in carbon nanoscience is to decipher formation mechanisms of highly ordered systems. Here, we disclose chemical processes that result in formation of high-symmetry clusterfullerenes, which attract interest for use in applications that span biomedicine to molecular electronics. The conversion of doped graphite into a C80 cage is shown to occur through bottom-up self-assembly reactions. Unlike conventional forms of fullerene, the iconic Buckminsterfullerene cage, I h-C60, is entirely avoided in the bottom-up formation mechanism to afford synthesis of group 3-based metallic nitride clusterfullerenes. The effects of structural motifs and cluster-cage interactions on formation of compounds in the solvent-extractable C70-C100 region are determined by in situ studies of defined clusterfullerenes under typical synthetic conditions. This work establishes the molecular origin and mechanism that underlie formation of unique carbon cage materials, which may be used as a benchmark to guide future nanocarbon explorations.

Regiochemically Controlled Synthesis of a ß-4-ß' [70]Fullerene Bis-Adduct.

A ß-4-ß' C70 bis-adduct regioisomer and an uncommon mono-adduct ß-malonate C70 derivative were synthesized by using a Diels-Alder cycloaddition followed by an addition-elimination of bromo-ethylmalonate and a retro-Diels-Alder cycloaddition reaction. We also report the regioselective synthesis and spectroscopic characterization of Cs-symmetric tris- and C2v-symmetric tetra-adducts of C70, which are the precursors of the mono- and bis-adduct final products.

Zigzag Sc2C2 Carbide Cluster inside a [88]Fullerene Cage with One Heptagon, Sc2C2@Cs(hept)-C88: A Kinetically Trapped Fullerene Formed by C2 Insertion?

A non-isolated pentagon rule metallic carbide clusterfullerene containing a heptagonal ring, Sc2C2@Cs(hept)-C88, was isolated from the raw soot obtained by electric arc vaporization of graphite rods packed with Sc2O3 and graphite powder under a helium atmosphere. The Sc2C2@Cs(hept)-C88 was purified by multistage high-performance liquid chromatography (HPLC), cocrystallized with Ni-(octaethylporphyrin), and characterized by single-crystal X-ray diffraction. The diffraction data revealed a zigzag Sc2C2 unit inside an unprecedented Cs(hept)-C88 carbon cage containing 13 pentagons, 32 hexagons, and 1 heptagon. Calculations suggest that the observed nonclassical fullerene could be a kinetically trapped species derived from the recently reported Sc2C2@C2v(9)-C86 via a direct C2 insertion.

Fullerene Derivatives Strongly Inhibit HIV-1 Replication by Affecting Virus Maturation without Impairing Protease Activity.

Three compounds (1, 2, and 3) previously reported to inhibit HIV-1 replication and/or in vitro activity of reverse transcriptase were studied, but only fullerene derivatives 1 and 2 showed strong antiviral activity on the replication of HIV-1 in human CD4(+) T cells. However, these compounds did not inhibit infection by single-round infection vesicular stomatitis virus glycoprotein G (VSV-G)-pseudotyped viruses, indicating no effect on the early steps of the viral life cycle. In contrast, analysis of single-round infection VSV-G-pseudotyped HIV-1 produced in the presence of compound 1 or 2 showed a complete lack of infectivity in human CD4(+) T cells, suggesting that the late stages of the HIV-1 life cycle were affected. Quantification of virion-associated viral RNA and p24 indicates that RNA packaging and viral production were unremarkable in these viruses. However, Gag and Gag-Pol processing was affected, as evidenced by immunoblot analysis with an anti-p24 antibody and the measurement of virion-associated reverse transcriptase activity, ratifying the effect of the fullerene derivatives on virion maturation of the HIV-1 life cycle. Surprisingly, fullerenes 1 and 2 did not inhibit HIV-1 protease in an in vitro assay at the doses that potently blocked viral infectivity, suggesting a protease-independent mechanism of action. Highlighting the potential therapeutic relevance of fullerene derivatives, these compounds block infection by HIV-1 resistant to protease and maturation inhibitors.

The Regioselectivity of Bingel-Hirsch Cycloadditions on Isolated Pentagon Rule Endohedral Metallofullerenes.

In this work, the Bingel-Hirsch addition of diethylbromomalonate to all non-equivalent bonds of Sc3N@D3h -C78 was studied using density functional theory calculations. The regioselectivities observed computationally allowed the proposal of a set of rules, the predictive aromaticity criteria (PAC), to identify the most reactive bonds of a given endohedral metallofullerene based on a simple evaluation of the cage structure. The predictions based on the PAC are fully confirmed by both the computational and experimental exploration of the Bingel-Hirsch reaction of Sc3N@D5h -C80, thus indicating that these rules are rather general and applicable to other isolated pentagon rule endohedral metallofullerenes.