In Situ Mapping and Local Negative Uptake Behavior of Adsorbates in Individual Pores of Metal-Organic Frameworks.

Herein, we report the adsorbate behavior in individual local pores of MIL-101, which is a metal-organic framework (MOF) with two heterogeneous mesopores and different metal sites, by combining adsorbate isotherms and in situ crystallography profiles. The in situ mapping shows that the substrate-adsorbate interaction affects the initial adsorption and pore condensation steps. The monolayer adsorption gradient changes greatly depending on the framework metal-adsorbate attraction force. Also, broad inflection points are found in adsorption isotherms, and the initial shape depends on the different metals. Besides, the capillary condensation at a pore draws adsorbates from other local pores. This leads to the local negative uptake behavior in individual pore isotherms. At higher pressure, they move to a larger space, whereas in a relatively low-pressure range the attraction force between the MOF framework and guest molecule influences the amount of rearranged guest molecules. Furthermore, the origin of the characteristic adsorption behavior based on the metals constituting the MOFs and the relative strength of substrate-adsorbate and adsorbate-adsorbate interactions are elucidated through the combined study of electron densities in pores, electron paramagnetic resonance spectroscopy spectra, and density functional theory and Monte Carlo simulations to uncover the previously veiled information on adsorption behavior.

Physicochemical Understanding of the Impact of Pore Environment and Species of Adsorbates on Adsorption Behaviour.

For a better design of adsorbents, it is important to know the intermolecular interaction among adsorbates and host material, leading to improved guest selectivity and uptake capacity. In this study, we demonstrate the influence of the interaction among adsorbates and substrate, controlled by the pore environment and species of adsorbates, on the adsorption behaviour. We report the unique CO2 adsorption behaviour of MOF-205 due to distinct pore geometry. The precise analysis through gas-adsorption crystallography with molecular simulation shows that capillary condensation of CO2 in MOF-205 occurs preferentially in the large dodecahedral pore rather than the small tetrahedral pore, because the interaction of CO2 with MOF-205 framework is weaker than that among CO2 molecules, while Ar and N2 are sequentially filled into two different pores of MOF-205 according to their size. Comparison of the materials with different pore environments reveals that the relative strength of the adsorbate-adsorbate and adsorbate-substrate interaction gives rise to different shapes of isotherms.

Generic Strategy to Synthesize High-Tap Density Anode and Cathode Structures with Stratified Graphene Pliable Pockets via Monomeric Polymerization and Evaporation, and Their Utilization to Enable Ultrahigh Performance in Hybrid Energy Storages.

Hybrid energy storage systems have shown great promise for many applications; however, achieving high energy and power densities with long cycle stability remains a major challenge. Here, a strategy to synthesize high-tap density anode and cathode structures that yield ultrahigh performance in hybrid energy storage is reported. First, vinyl acetate monomers are polymerized into molecular sizes via chain reactions controlled by the surface free radicals of graphene and metals. Subsequently, molecular-size polymers are thermally evaporated to construct battery-type anode structures with encapsulated tin metals for high-capacity and stratified graphene pliable pockets (GPPs) for fast charge transfer. Similarly, sulfur particles are attached to GPPs via monomeric polymerization, and capacitor-type hollow GPP (H@GPP) cathode structures are produced by evaporating sulfur, where sublimated S particles yield mesopores for rapid anion movement and micropores for high capacity. Moreover, hybrid full-cell devices with high-tap density anodes and cathodes show high gravimetric energy densities of up to 206.9 Wh kg-1 , exceeding those of capacitors by ≈16-fold, and excellent volumetric energy densities of up to 92.7 Wh L-1 . Additionally, they attain high power densities of up to 23 678 W kg-1 , outperforming conventional devices by a factor of ≈100, and long cycle stability over 10 000 cycles.

Ultrafine Metallic Nickel Domains and Reduced Molybdenum States Improve Oxygen Evolution Reaction of NiFeMo Electrocatalysts.

An electrocatalyst for oxygen evolution reaction (OER) is essential in the realization of renewable energy conversion technologies, but its large overpotential, slow charge transfer, and degradation of surface reaction sites are yet to be overcome. Here, it is found that the metallic nickel domains and high-valence reduced molybdenum ions of NiFeMo electrocatalysts grown on a 3D conductive and porous electrode without using binders enable ultrahigh performance in OER. High resolution-transmission electron microscope and extended X-ray absorption fine structure analyses show that metallic nickel domains with Ni-Ni bonds are generated on the catalyst surface via a dry synthesis using nitrogen plasma. Also, Mo K-edge X-ray absorption near-edge spectroscopy reveals that Mo6+ ions are reduced into high-valence modulating Mo4+ ions. With the metallic nickel domains facilitating the adsorption of oxygen intermediates to low-coordinated Ni0 and the Mo4+ pulling their electrons, the catalyst exhibits about 60-fold higher activity than a Mo-free NiFe catalyst, while giving about threefold faster charge transfer along with longer stability over 100 h and repeated 100 cycles compared to a bare NiFeMo catalyst. Additionally, these metallic domains and high-valence modulating metal ions are exhibited to give high Faradaic efficiency over 95%.

Rescaling of metal oxide nanocrystals for energy storage having high capacitance and energy density with robust cycle life.

Nanocrystals are promising structures, but they are too large for achieving maximum energy storage performance. We show that rescaling 3-nm particles through lithiation followed by delithiation leads to high-performance energy storage by realizing high capacitance close to the theoretical capacitance available via ion-to-atom redox reactions. Reactive force-field (ReaxFF) molecular dynamics simulations support the conclusion that Li atoms react with nickel oxide nanocrystals (NiO-n) to form lithiated core-shell structures (Ni:Li2O), whereas subsequent delithiation causes Ni:Li2O to form atomic clusters of NiO-a. This is consistent with in situ X-ray photoelectron and optical spectroscopy results showing that Ni(2+) of the nanocrystal changes during lithiation-delithiation through Ni(0) and back to Ni(2+). These processes are also demonstrated to provide a generic route to rescale another metal oxide. Furthermore, assembling NiO-a into the positive electrode of an asymmetric device enables extraction of full capacitance for a counter negative electrode, giving high energy density in addition to robust capacitance retention over 100,000 cycles.

Broadband Light Absorption and Efficient Charge Separation Using a Light Scattering Layer with Mixed Cavities for High-Performance Perovskite Photovoltaic Cells with Stability.

CH3 NH3 PbI3 is one of the promising light sensitizers for perovskite photovoltaic cells, but a thick layer is required to enhance light absorption in the long-wavelength regime ranging from PbI2 absorption edge (500 nm) to its optical band-gap edge (780 nm) in visible light. Meanwhile, the thick perovskite layer suppresses visible-light absorption in the short wavelengths below 500 nm and charge extraction capability of electron-hole pairs produced upon light absorption. Herein, we find that a new light scattering layer with the mixed cavities of sizes in 100 and 200 nm between transparent fluorine-doped tin oxide and mesoporous titanium dioxide electron transport layer enables full absorption of short-wavelength photons (λ < 500 nm) to the perovskite along with enhanced absorption of long-wavelength photons (500 nm < λ < 780 nm). Moreover, the light-driven electric field is proven to allow efficient charge extraction upon light absorption, thereby leading to the increased photocurrent density as well as the fill factor prompted by the slow recombination rate. Additionally, the photocurrent density of the cell with a light scattering layer of mixed cavities is stabilized due to suppressed charge accumulation. Consequently, this work provides a new route to realize broadband light harvesting of visible light for high-performance perovskite photovoltaic cells.

3D nitrogen-doped carbon frameworks with hierarchical pores and graphitic carbon channels for high-performance hybrid energy storages.

In principle, hybrid energy storages can utilize the advantages of capacitor-type cathodes and battery-type anodes, but their cathode and anode materials still cannot realize a high energy density, fast rechargeable capability, and long-cycle stability. Herein, we report a strategy to synthesize cathode and anode materials as a solution to overcome this challenge. Firstly, 3D nitrogen-doped hierarchical porous graphitic carbon (NHPGC) frameworks were synthesized as cathode materials using Co-Zn mixed metal-organic frameworks (MOFs). A high capacity is achieved due to the abundant nitrogen and micropores produced by the MOF nanocages and evaporation of Zn. Also, fast ion/electron transport channels were derived through the Co-catalyzed hierarchical porosity control and graphitization. Moreover, tin oxide precursors were introduced in NHPGC to form the SnO2@NHPGC anode. Operando X-ray diffraction revealed that the rescaled subnanoparticles as anodic units facilitated the high capacity during ion insertion-induced rescaling. Besides, the Sn-N bonds endowed the anode with a cycling stability. Furthermore, the NHPGC cathode and SnO2@NHPGC achieved an ultrahigh energy density (up to 244.5 W h kg-1 for Li and 146.1 W h kg-1 for Na), fast rechargeable capability (up to 93C-rate for Li and 147C-rate for Na) as exhibited by photovoltaic recharge within a minute and a long-cycle stability with ∼100% coulombic efficiency over 10 000 cycles.

A hydrogen radical pathway for efficacious electrochemical nitrate reduction to ammonia over an Fe-polyoxometalate/Cu electrocatalyst.

Electrochemical nitrate (NO3-) reduction to ammonia (NH3), which is a high value-added chemical or high-energy density carrier in many applications, could become a key process overcoming the disadvantages of the Haber-Bosch process; however, current electrocatalysts have severe drawbacks in terms of activity, selectivity, and stability. Here, we report the hydrogen radical (H*) pathway as a solution to overcome this challenge, as demonstrated by efficacious electrochemical NO3- reduction to NH3 over the Fe-polyoxometalate (Fe-POM)/Cu hybrid electrocatalyst. Fe-POM, composed of Preyssler anions ([NaP5W30O110]14-) and Fe cations, facilitates efficient H* generation via H2O + e- → H* + OH-, and H* transfer to the Cu sites of the Fe-POM/Cu catalyst enables selective NO3- reduction to NH3. Operando spectroelectrochemical spectra substantiate the occurrence of the H* pathway through direct observation of Fe redox related to H* generation and Cu redox related to NO3- binding. With the H* pathway, the Fe-POM/Cu electrodes exhibit high activity for NO3- reduction to NH3 with 1.44 mg cm-2 h-1 in a 500 ppm NO3-/1 M KOH solution at -0.2 V vs. RHE, which is about 36-fold higher than that of the pristine Cu electrocatalyst. Additionally, it attains high selectivity with a faradaic efficiency of up to 97.09% at -0.2 V vs. RHE while exhibiting high catalytic stability over cycles.

Nitrogen-doped multiwall carbon nanotubes for lithium storage with extremely high capacity.

The increasing demands on high performance energy storage systems have raised a new class of devices, so-called lithium ion capacitors (LICs). As its name says, LIC is an intermediate system between lithium ion batteries and supercapacitors, designed for taking advantages of both types of energy storage systems. Herein, as a quest to improve the Li storage capability compared to that of other existing carbon nanomaterials, we have developed extrinsically defective multiwall carbon nanotubes by nitrogen-doping. Nitrogen-doped carbon nanotubes contain wall defects through which lithium ions can diffuse so as to occupy a large portion of the interwall space as storage regions. Furthermore, when integrated with 3 nm nickel oxide nanoparticles for a further capacity boost, nitrogen doping enables unprecedented cell performance by engaging anomalous electrochemical phenomena such as nanoparticles division into even smaller ones, their agglomeration-free diffusion between nitrogen-doped sites as well as capacity rise with cycles. The final cells exhibit a capacity as high as 3500 mAh/g, a cycle life of greater than 10,000 times, and a discharge rate capability of 1.5 min while retaining a capacity of 350 mAh/g.

3D Porous Oxygen-Doped and Nitrogen-Doped Graphitic Carbons Derived from Metal Azolate Frameworks as Cathode and Anode Materials for High-Performance Dual-Carbon Sodium-Ion Hybrid Capacitors.

Sodium-ion hybrid capacitors (SIHCs) in principle can utilize the advantages of batteries and supercapacitors and satisfy the cost demand of large-scale energy storage systems, but the sluggish kinetics and low capacities of its anode and cathode are yet to be overcome. Here, a strategy is reported to realize high-performance dual-carbon SIHCs using 3D porous graphitic carbon cathode and anode materials derived from metal-azolate framework-6s (MAF-6s). First, MAF-6s, with or without urea loading, are pyrolyzed to synthesize MAF-derived carbons (MDCs). Then, cathode materials are synthesized via the controlled KOH-assisted pyrolysis of MDCs (K-MDCs). K-MDCs, 3D graphitic carbons, resulting in a record-high surface area (5214 m2  g-1 ) being ≈four-fold higher than pristine MAF-6, oxygen-doped sites for high capacity, rich mesopores affording fast ion transport, and high capacity retention over 5000 charge/discharge cycles. Moreover, 3D porous MDC anode materials are synthesized from N-containing MAF-6 and exhibited to allow cycle stability over 5000 cycles. Furthermore, dual-carbon MDC//K-MDC SIHCs with different loadings (3 to 6 mg cm-2 ) are demonstrated to achieve high energy densities exceeding those of sodium-ion batteries and supercapacitors. Additionally, it allows an ultrafast-chargeable high power density of 20000 W kg-1 and robust cycle stability overcoming those of a typical battery.

Direct photocatalytic patterning of colloidal emissive nanomaterials.

We present a universal direct photocatalytic patterning method that can completely preserve the optical properties of perovskite nanocrystals (PeNCs) and other emissive nanomaterials. Solubility change of PeNCs is achieved mainly by a photoinduced thiol-ene click reaction between specially tailored surface ligands and a dual-role photocatalytic reagent, pentaerythritol tetrakis(3-mercaptopropionate) (PTMP), where the thiol-ene reaction is enabled at a low light intensity dose (~ 30 millijoules per square centimeter) by the strong photocatalytic activity of PeNCs. The photochemical reaction mechanism was investigated using various analyses at each patterning step. The PTMP also acts as a defect passivation agent for the PeNCs and even enhances their photoluminescence quantum yield (by ~5%) and photostability. Multicolor patterns of cesium lead halide (CsPbX3)PeNCs were fabricated with high resolution (<1 micrometer). Our method is widely applicable to other classes of nanomaterials including colloidal cadmium selenide-based and indium phosphide-based quantum dots and light-emitting polymers; this generality provides a nondestructive and simple way to pattern various functional materials and devices.

Site-specific transition metal occupation in multicomponent pyrophosphate for improved electrochemical and thermal properties in lithium battery cathodes: a combined experimental and theoretical study.

As an attempt to develop lithium ion batteries with excellent performance, which is desirable for a variety of applications including mobile electronics, electrical vehicles, and utility grids, the battery community has continuously pursued cathode materials that function at higher potentials with efficient kinetics for lithium insertion and extraction. By employing both experimental and theoretical tools, herein we report multicomponent pyrophosphate (Li(2)MP(2)O(7), M = Fe(1/3)Mn(1/3)Co(1/3)) cathode materials with novel and advantageous properties as compared to the single-component analogues and other multicomponent polyanions. Li(2)Fe(1/3)Mn(1/3)Co(1/3)P(2)O(7) is formed on the basis of a solid solution among the three individual transition-metal-based pyrophosphates. The unique crystal structure of pyrophosphate and the first principles calculations show that different transition metals have a tendency to preferentially occupy either octahedral or pyramidal sites, and this site-specific transition metal occupation leads to significant improvements in various battery properties: a single-phase mode for Li insertion/extraction, improved cell potentials for Fe(2+)/Fe(3+) (raised by 0.18 eV) and Co(2+)/Co(3+) (lowered by 0.26 eV), and increased activity for Mn(2+)/Mn(3+) with significantly reduced overpotential. We reveal that the favorable energy of transition metal mixing and the sequential redox reaction for each TM element with a sufficient redox gap is the underlying physical reason for the preferential single-phase mode of Li intercalation/deintercalation reaction in pyrophosphate, a general concept that can be applied to other multicomponent systems. Furthermore, an extremely small volume change of ~0.7% between the fully charged and discharged states and the significantly enhanced thermal stability are observed for the present material, the effects unseen in previous multicomponent battery materials.

Fermi energy level tuning for high performance dye sensitized solar cells using sp2 selective nitrogen-doped carbon nanotube channels.

Here, we find that doping sp(2) selective nitrogen, N sp(2), into carbon nanotube (CNT) channels induces a positive shift in the Fermi level of TiO(2) photoelectrodes. It is found that this results in the large diffusion coefficient of solar driven electrons for increasing the photocurrent as well as in the low recombination rate for improving open circuit voltage with 0.74 V, which could not be overcome by using pristine CNT channels with 0.66 V.

Nitrogen-doped graphene for high-performance ultracapacitors and the importance of nitrogen-doped sites at basal planes.

Although various carbon nanomaterials including activated carbon, carbon nanotubes, and graphene have been successfully demonstrated for high-performance ultracapacitors, their capacitances need to be improved further for wider and more challenging applications. Herein, using nitrogen-doped graphene produced by a simple plasma process, we developed ultracapacitors whose capacitances (∼280 F/g(electrode)) are about 4 times larger than those of pristine graphene based counterparts without sacrificing other essential and useful properties for ultracapacitor operations including excellent cycle life (>200,000), high power capability, and compatibility with flexible substrates. While we were trying to understand the improved capacitance using scanning photoemission microscopy with a capability of probing local nitrogen-carbon bonding configurations within a single sheet of graphene, we observed interesting microscopic features of N-configurations: N-doped sites even at basal planes, distinctive distributions of N-configurations between edges and basal planes, and their distinctive evolutions with plasma duration. The local N-configuration mappings during plasma treatment, alongside binding energy calculated by density functional theory, revealed that the origin of the improved capacitance is a certain N-configuration at basal planes.

Fast Charge Transfer and High Stability via Hybridization of Hygroscopic Cu-BTC Metal-Organic Framework Nanocrystals with a Light-Absorbing Layer for Perovskite Solar Cells.

Perovskite solar cells (PSCs) have great potential as an efficient solar energy harvesting system due to their outstanding optoelectronic properties, but the charge accumulation and recombination, as well as the moisture-induced degradation of the light-absorbing perovskite layers, remain great bottlenecks in practical applications for future technology. As a solution to this challenge, here we report a strategy to realize moisture-stable PSCs allowing fast charge transfer that, in turn, leads to high power conversion efficiency (PCE). Hybridization of hygroscopic copper(II) benzene-1,3,5-tricarboxylate metal-organic frameworks (Cu-BTC MOFs) with a light-absorbing perovskite layer for PSCs, where a moderate level of moisture attracted by Cu-BTC MOFs during the synthesis step, leads to enhanced perovskite crystallization. Besides, the perovskite-MOF hybrid facilitates the transfer of photoexcited electrons from the perovskite to TiO2 by providing additional channels for electron extraction. This enables a high PCE of 20.5% in a triple-cation perovskite-MOF device with negligible hysteresis compared to reference devices. Moreover, the perovskite-MOF hybrid exhibits high stability in ambient air under dark conditions over a long period (up to 22 months), while the unmodified counterpart quickly decomposes into PbI2. Consequently, this work provides a promising clue to realizeing fast charge transfer and high stability for high-performance PSCs.

Coiled Conformation Hollow Carbon Nanosphere Cathode and Anode for High Energy Density and Ultrafast Chargeable Hybrid Energy Storage.

Lithium-ion batteries and pseudocapacitors are nowadays popular electrochemical energy storage for many applications, but their cathodes and anodes are still limited to accommodate rich redox ions not only for high energy density but also sluggish ion diffusivity and poor electron conductivity, hindering fast recharge. Here, we report a strategy to realize high-capacity/high-rate cathode and anode as a solution to this challenge. Multiporous conductive hollow carbon (HC) nanospheres with microporous shells for high capacity and hollow cores/mesoporous shells for rapid ion transfer are synthesized as cathode materials using quinoid:benzenoid (Q:B) unit resins of coiled conformation, leading to ∼5-fold higher capacities than benzenoid:benzenoid resins of linear conformation. Also, Ge-embedded Q:B HC nanospheres are derived as anode materials. The atomic configuration and energy storage mechanism elucidate the existence of mononuclear GeOx units giving ∼7-fold higher ion diffusivity than bulk Ge while suppressing volume changes during long ion-insertion/desertion cycles. Moreover, hybrid energy storage with a Q:B HC cathode and Ge-Q:B HC anode exploit the advantages of capacitor-type cathode and battery-type anode electrodes, as exhibited by battery-compatible high energy density (up to 285 Wh kg-1) and capacitor-compatible ultrafast rechargeable power density (up to 22 600 W kg-1), affording recharge within a minute.

Heterogeneity within order in crystals of a porous metal-organic framework.

Generally, crystals of synthetic porous materials such as metal-organic frameworks (MOFs) are commonly made up from one kind of repeating pore structure which predominates the whole material. Surprisingly, little is known about how to introduce heterogeneously arranged pores within a crystal of homogeneous pores without losing the crystalline nature of the material. Here, we outline a strategy for producing crystals of MOF-5 in which a system of meso- and macropores either permeates the whole crystal to make sponge-like crystals or is entirely enclosed by a thick crystalline microporous MOF-5 sheath to make pomegranate-like crystals. These new forms of crystals represent a new class of materials in which micro-, meso-, and macroporosity are juxtaposed and are directly linked unique arrangements known to be useful in natural systems but heretofore unknown in synthetic crystals.

Strain-Induced Metallization and Defect Suppression at Zipper-like Interdigitated Atomically Thin Interfaces Enabling High-Efficiency Halide Perovskite Solar Cells.

Halide perovskite light absorbers have great advantages for photovoltaics such as efficient solar energy absorption, but charge accumulation and recombination at the interface with an electron transport layer (ETL) remain major challenges in realizing the absorbers' full potential. Here we report the experimental realization of a zipper-like interdigitated interface between a Pb-based halide perovskite light absorber and an oxide ETL by the PbO capping of the ETL surface, which produces an atomically thin two-dimensional metallic layer that can significantly enhance the perovskite/ETL charge extraction process. As the atomistic origin of the emergent two-dimensional interfacial metallicity, first-principles calculations performed on the representative MAPbI3/TiO2 interface identify the interfacial strain induced by the simultaneous formation of stretched I-substitutional Pb bonds (and thus Pb-I-Pb bonds bridging MAPbI3 and TiO2) and contracted substitutional Pb-O bonds. Direct and indirect experimental evidence for the presence of interfacial metallic states are provided, and a nonconventional defect-passivating nature of the strained interdigitated perovskite/ETL interface is emphasized. It is experimentally demonstrated that the PbO capping method is generally applicable to other ETL materials, including ZnO and SrTiO3, and that the zipper-like interdigitated metallic interface leads to about a 2-fold increase in the charge extraction rate. Finally, in terms of the photovoltaic efficiency, we observe a volcano-type behavior with the highest performance achieved at the monolayer-level PbO capping. This work establishes a general perovskite/ETL interface engineering approach to realize high-performance perovskite solar cells.

Metal-Organic Fragments with Adhesive Excipient and Their Utilization to Stabilize Multimetallic Electrocatalysts for High Activity and Robust Durability in Oxygen Evolution Reaction.

Multimetallic electrocatalysts have shown great potential to improve electrocatalytic performance, but their deteriorations in activity and durability are yet to be overcome. Here, metal-organic fragments with adhesive excipient to realize high activity with good durability in oxygen evolution reaction (OER) are developed. First, a leaf-like zeolitic-imidazolate framework (ZIF-L) is synthesized. Then, ionized species in hydrogen plasma attack preferentially the organic linkers of ZIF-L to derive cobalt-imidazole fragments (CIFs) as adhesive excipient, while they are designed to retain the coordinated cobalt nodes. Moreover, the vacant coordination sites at cobalt nodes and the unbound nitrogen at organic linkers induce high porosity and conductivity. The CIFs serve to stably impregnate trimetallic FeNiMo electrocatalysts (CIF:FeNiMo), and CIF:FeNiMo containing Fe contents of 22% and hexavalent Mo contents show to enable high activity with low overpotentials (203 mV at 10 mA cm-2 and 238 mV at 100 mA cm-2 ) in OER. The near O K-edge extended X-ray absorption fine structure proves further that high activity for OER originates from the partially filled eg orbitals. Additionally, CIF:FeNiMo exhibit good durability, as demonstrated by high activity retention during at least 45 days in OER.

Selective synthesis of diameter- and interlayer-controlled carbon nitride nanotubes with hydrogen ensnaring nanopores.

Diameter- and interlayer-controlled carbon nitride nanotubes (CNNTs) having nanopores with approximately 6 A diameters are synthesized by our new plasma-assisted growth method on catalysts located inside the organic silica mesoporous templates. Our experiments and first-principles calculations show that hydrogen stored inside nanopores of 6.2 A are attributed to the hydrogen released at 257.24 K.