Feeble Single-Atom Pd Catalysts for H2 Production from Formic Acid.

Single-atom catalysts are thought to be the pinnacle of catalysis. However, for many reactions, their suitability has yet to be unequivocally proven. Here, we demonstrate why single Pd atoms (PdSA) are not catalytically ideal for generating H2 from formic acid as a H2 carrier. We loaded PdSA on three silica substrates, mesoporous silicas functionalized with thiol, amine, and dithiocarbamate functional groups. The Pd catalytic activity on amino-functionalized silica (SiO2-NH2/PdSA) was far higher than that of the thiol-based catalysts (SiO2-S-PdSA and SiO2-NHCS2-PdSA), while the single-atom stability of SiO2-NH2/PdSA against aggregation after the first catalytic cycle was the weakest. In this case, Pd aggregation boosted the reaction yield. Our experiments and calculations demonstrate that PdSA in SiO2-NH2/PdSA loosely binds with amine groups. This leads to a limited charge transfer from Pd to the amine groups and causes high aggregability and catalytic activity. According to the density functional calculations, the loose binding between Pd and N causes most of Pd's 4d electrons in amino-functionalized SiO2 to remain close to the Fermi level and labile for catalysis. However, PdSA chemically binds to the thiol group, resulting in strong hybridization between Pd and S, pulling Pd's 4d states deeper into the conduction band and away from the Fermi level. Consequently, fewer 4d electrons were available for catalysis.

Single-Atom Sn-Loaded Exfoliated Layered Titanate Revealing Enhanced Photocatalytic Activity in Hydrogen Generation.

Green H2 generation through layered materials plays a significant role among a wide variety of materials owing to their high theoretical surface area and distinctive features in (photo)catalysis. Layered titanates (LTs) are a class of these materials, but they suffer from large bandgaps and a layers' stacked form. We first address the successful exfoliation of bulk LT to exfoliated few-layer sheets via long-term dilute HCl treatment at room temperature without any organic exfoliating agents. Then, we demonstrate a substantial photocatalytic activity enhancement through the loading of Sn single atoms on exfoliated LTs (K0.8Ti1.73Li0.27O4). Comprehensive analysis, including time-resolved photoluminescence spectroscopy, revealed the modification of electronic and physical properties of the exfoliated layered titanate for better solar photocatalysis. Upon treating the exfoliated titanate in SnCl2 solution, a Sn single atom was successfully loaded on the exfoliated titanate, which was characterized by spectroscopic and microscopic techniques, including aberration-corrected transmission electron microscopy. The exfoliated titanate with an optimal Sn loading exhibited a good photocatalytic H2 evolution from water containing methanol and from ammonia borane (AB) dehydrogenation, which was not only enhanced from the pristine LT, but higher than conventional TiO2-based photocatalysts like Au-loaded P25.

MOF-derived nanocrystalline ZnO with controlled orientation and photocatalytic activity.

We show here that MOF-5, a sample Zn-based MOF, can uniquely transform into distinct zinc oxide nanostructures. Inspired by the interconversion synthesis of zeolites, we converted MOF-5 into nanocrystalline ZnO. We found the conversion of MOF-5 into ZnO to be tunable and straightforward simply by controlling the treatment temperature and choosing an appropriate structure-directing agent (SDA). Refined X-ray diffraction (XRD) patterns showed that a synthesis temperature of 180 °C (sample ZnO-180) was optimal for achieving high crystallinity. We examined ZnO-180 with high-resolution transmission electron microscopy (HRTEM), which confirmed that the samples were made of individual crystallites grown along the c-axis, or the (001) direction, thus exposing lower energy surfaces and corroborating the XRD pattern and the molecular dynamics calculations. Further investigations revealed that the obtained ZnO at 180 °C has a superior photocatalytic activity in degrading methylene blue to other ZnO nanostructures obtained at lower temperatures.

Phenyl-Modified Carbon Nitride Quantum Nanoflakes for Ultra-Highly Selective Sensing of Formic Acid: A Combined Experimental by QCM and Density Functional Theory Study.

Formic acid (HCOOH) is an important intermediate in chemical synthesis, pharmaceuticals, the food industry, and leather tanning and is considered to be an effective hydrogen storage molecule. Direct contact with its vapor and its inhalation lead to burns, nerve injury, and dermatosis. Thus, it is critical to establish efficient sensing materials and devices for the rapid detection of HCOOH. In the present study, we introduce a chemical sensor based on a quartz crystal microbalance (QCM) sensor capable of detecting trace amounts of HCOOH. This sensor is composed of colloidal phenyl-terminated carbon nitride (Ph-g-C3N4) quantum nanoflakes prepared using a facile solid-state method involving the supramolecular preorganization technology. In contrast to other synthetic methods of modified carbon nitride materials, this approach requires no hard templates, hazardous chemicals, or hydrothermal treatments. Comprehensive characterization and density functional theory (DFT) calculations revealed that the QCM sensor designed and prepared here exhibits enhanced detection sensitivity and selectivity for volatile HCOOH, which originates from chemical and hydrogen-bonding interactions between HCOOH and the surface of Ph-g-C3N4. According to DFT results, HCOOH is located close to the cavity of the Ph-g-C3N4 unit, with bonding to graphitic carbon and pyridinic nitrogen atoms of the nanoflake. The sensitivity of the Ph-g-C3N4-nanoflake-based QCM sensor was found to be the highest (128.99 Hz ppm-1) of the substances studied, with a limit of detection (LOD) of HCOOH down to a sub-ppm level of 80 ppb. This sensing technology based on phenyl-terminated attached-g-C3N4 nanoflakes establishes a simple, low-cost solution to improve the performance of QCM sensors for the effective discrimination of HCOOH, HCHO, and CH3COOH vapors using smart electronic noses.

Bispropylurea bridged polysilsesquioxane: A microporous MOF-like material for molecular recognition.

Microporous organosilicas assembled from polysilsesquioxane (POSS) building blocks are promising materials that are yet to be explored in-depth. Here, we investigate the processing and molecular structure of bispropylurea bridged POSS (POSS-urea), synthesised through the acidic condensation of 1,3-bis(3-(triethoxysilyl)propyl)urea (BTPU). Experimentally, we show that POSS-urea has excellent functionality for molecular recognition toward acetonitrile with an adsorption level of 74 mmol/g, which compares favourably to MOFs and zeolites, with applications in volatile organic compounds (VOC). The acetonitrile adsorption capacity was 132-fold higher relative to adsorption capacity for toluene, which shows the pores are highly selective towards acetonitrile adsorption due to their size and arrangement. Theoretically, our tight-binding density functional and molecular dynamics calculations demonstrated that this BTPU based POSS is microporous with an irregular placement of the pores. Structural studies confirm maximal pore sizes of ∼1 nm, with POSS cages possessing an approximate edge length of ∼3.16 Å.

Holey Assembly of Two-Dimensional Iron-Doped Nickel-Cobalt Layered Double Hydroxide Nanosheets for Energy Conversion Application.

Layered double hydroxides (LDHs) containing first-row transition metals such as Fe, Co, and Ni have attracted significant interest for electrocatalysis owing to their abundance and excellent performance for the oxygen evolution reaction (OER) in alkaline media. Herein, the assembly of holey iron-doped nickel-cobalt layered double hydroxide (NiCo-LDH) nanosheets ('holey nanosheets') is demonstrated by employing uniform Ni-Co glycerate spheres as self-templates. Iron doping was found to increase the rate of hydrolysis of Ni-Co glycerate spheres and induce the formation of a holey interconnected sheet-like structure with small pores (1-10 nm) and a high specific surface area (279 m2 g-1 ). The optimum Fe-doped NiCo-LDH OER catalyst showed a low overpotential of 285 mV at a current density of 10 mA cm-2 and a low Tafel slope of 62 mV dec-1 . The enhanced OER activity was attributed to (i) the high specific surface area of the holey nanosheets, which increases the number of active sites, and (ii) the improved kinetics and enhanced ion transport arising from the iron doping and synergistic effects.

Template-oriented synthesis of hydroxyapatite nanoplates for 3D bone printing.

The design of hydroxyapatite (HA) nanoarchitecture is critical for fabricating artificial bone tissues as it dictates the biochemical and the mechanical properties of the final product. Herein, we incorporated a simple hard-template approach to synthesise single crystal nanoplates of HA. We used the 2D graphitic nitride (g-C3N4) material to prepare an HA sol-gel under hydrothermal conditions. A new HA nanostructure was then formed during the calcination and removal of g-C3N4 at a higher temperature, which finally led to the production of nanoplates (thickness of ∼100 nm) while in lateral dimension the average size was in the micrometre scale. We characterised the synthesised HA nanoplates with XRD, TEM, and HRTEM. The theoretically predicted nanostructure construction based on Wulff's method is in full agreement with the experimental observations. We then prepared different weight ratios of HA and polylactic acid (PLA) composites for artificial 3D bone fabrication. The strong interaction between PLA and HA's (110) facet, which was the second most prevalent, resulted in the composite's mechanical robustness. After mechanical testing, an optimum ratio was selected for biological studies and 3D printing. Biological experiments demonstrated that the synthesised composite had excellent viability in vitro.

Condensed ferric dimers for green photocatalytic synthesis of nylon precursors.

Although iron oxides have been extensively studied as photocatalysts because of their abundance and environmental compatibility, their performance is notoriously low due to factors such as low photoinduced charge-separation efficiency. Iron oxides, thus, must be modified with expensive and/or toxic materials to attain higher performances, which devalues their appeal as sustainable materials. Here, we design an iron oxide exhibiting an unprecedentedly high photocatalytic performance unrealized by previous photocatalysts such as TiO2 for reactions including the selective oxidation of cyclohexane to industrial nylon precursors. The iron oxide photocatalyst consists of ferric dimers, otherwise extremely unstable, formed via etching of Fe and O sites from ferric oxide nanoparticles immobilized within porous silica. We demonstrate a remarkably high photoinduced charge-separation efficiency (long lifetime of active species) of the ferric dimers due to their electronic structure and the potential of this supported photocatalyst for many more reactions.

Synthesis of Mesoporous TiO2-B Nanobelts with Highly Crystalized Walls toward Efficient H2 Evolution.

Mesoporous TiO2 is attracting increasing interest due to properties suiting a broad range of photocatalytic applications. Here we report the facile synthesis of mesoporous crystalline TiO2-B nanobelts possessing a surface area as high as 80.9 m2 g-1 and uniformly-sized pores of 6-8 nm. Firstly, P25 powders are dissolved in NaOH solution under hydrothermal conditions, forming sodium titanate (Na2Ti3O7) intermediate precursor phase. Then, H2Ti3O7 is successfully obtained by ion exchange through acid washing from Na2Ti3O7 via an alkaline hydrothermal treatment. After calcination at 450 °C, the H2Ti3O7 is converted to a TiO2-B phase. At 600 °C, another anatase phase coexists with TiO2-B, which completely converts into anatase when annealed at 750 °C. Mesoporous TiO2-B nanobelts obtained after annealing at 450 °C are uniform with up to a few micrometers in length, 50-120 nm in width, and 5-15 nm in thickness. The resulting mesoporous TiO2-B nanobelts exhibit efficient H2 evolution capability, which is almost three times that of anatase TiO2 nanobelts.

Conversion of a 2D Lepidocrocite-Type Layered Titanate into Its 1D Nanowire Form with Enhancement of Cation Exchange and Photocatalytic Performance.

Layered titanates with one-dimensional (1D) shapes have been an important class of nanomaterials due to their combination of 1D and 2D fascinating properties. Among many layered titanates, lepidocrocite-type layered titanates have significant advantages such as superior intercalation and exfoliation properties, while the synthesis of the 1D-shape forms is still challenging. Here, we report on a facile one-pot hydrothermal conversion of a lepidocrocite-type layered titanate into the corresponding nanowire-shape form. The reaction mechanism involves the decomposition of the starting layered titanate into 1D small segments which assemble into the nanowire. This new nanowire shows properties resulting from the combination of 1D and 2D nanostructural features, excellent cation exchange ability, and high photoinduced charge separation and photocatalytic efficiency. As a demonstration, we evaluate the nanowire as a sequestrating material capable of collecting toxic cations, like Cd2+, from water and photoreducing them (immobilizing them tightly). We find that the nanowire shows an efficient and ultrafast photoimmobilization activity, whereas the starting layered titanate and a benchmark TiO2 photocatalyst (P25) show no activity under the identical conditions. The photoimmobilization rate (within 1 min) is considerably faster than the cation exchange rates reported for state-of-the-art cation exchangers (with no photoimmobilization ability). The nanowire used for photoimmobilization reactions is easily recovered from water by decantation, showing the possible practical use for safe disposal of toxic cations in the environment.

Self-Supported ZIF-Derived Co3 O4 Nanoparticles-Decorated Porous N-Doped Carbon Fibers as Oxygen Reduction Catalyst.

Oxygen reduction is a significant cathodic reaction in the state-of-art clean energy devices such as fuel cell and metal-oxygen battery. Here, ZIF-incorporated hybrid polymeric fibres have been fabricated by using a dual-phase electrospinning method. These are then transformed into Co3 O4 -nanoparticle-decorated porous N-doped carbon fibres (ZIF-Co3 O4 /NCF) through multi-step annealing treatment. The resultant ZIF-Co3 O4 /NCF is interweaved into a self-supported film and can be used as a bi-functional catalyst for catalysing oxygen reduction in both aqueous and non-aqueous electrolytes. Electrochemical tests demonstrate that ZIF-Co3 O4 /NCF displays a high catalytic activity for oxygen reduction with a half-wave potential (E1/2 ) of 0.813 V (vs. RHE) and an almost favourable four-electron reduction pathway in alkaline medium. ZIF-Co3 O4 /NCF catalyst only shows 4 mV negative shift of E1/2 after 5000 continuous CV cycles. In addition, the ZIF-Co3 O4 /NCF can be applied as the cathode catalyst of non-aqueous Li-O2 battery, exhibiting a remarkable ORR activity in LiPF6 contained 1,2-dimethoxyethane electrolyte. The excellent electrocatalytic performance of ZIF-Co3 O4 /NCF is probably due to the abundance of active sites of graphitic carbon-wrapped Co3 O4 nanoparticles, as well as the cross-linked fibrous nitrogen-doped carbon texture.

Development of Sulfonic-Acid-Functionalized Mesoporous Materials: Synthesis and Catalytic Applications.

Sulfonic acid based mesostructures (SAMs) have been developed in recent years and have important catalytic applications. The primary applications of these materials are in various organic synthesis reactions, such as multicomponent reactions, carbon-carbon bond couplings, protection reactions, and Fries and Beckman rearrangements. This review aims to provide an overview of the recent developments in the field of SAMs with a particular emphasis on the reaction scope and advantages of heterogeneous solid acid catalysts.

Iron phosphide anchored nanoporous carbon as an efficient electrode for supercapacitors and the oxygen reduction reaction.

Inspired by their distinctive properties, transition metal phosphides have gained immense attention as promising electrode materials for energy storage and conversion applications. The introduction of a safe and large-scale method of synthesizing a composite of these materials with carbon is of great significance in the fields of electrochemical and materials sciences. In the current effort, we successfully synthesize an iron phosphide/carbon (FeP/C) with a high specific surface area by the pyrolysis of the gel resulting from the hydrothermal treatment of an iron nitrate-phytic acid mixed solution. In comparison with the blank (P/C), the as-synthesized FeP/C appears to be an efficient electrode material for supercapacitor as well as oxygen reduction reaction (ORR) applications in an alkaline medium in a three-electrode system. In the study of supercapacitors, FeP/C shows areal capacitance of 313 mF cm-2 at 1.2 mA cm-2 while retaining 95% of its initial capacitance value after 10 000 cycles, while in the ORR, the synthesized material exhibits high electrocatalytic activity with an onset potential of ca. 0.86 V vs. RHE through the preferred four-electron pathway and less than 6% H2O2 production calculated in the potential range of 0.0-0.7 V vs. RHE. The stability is found to be better than those of the benchmark Pt/C (20 wt%) catalyst.

Pore shape-reflecting morphosynthesis of lithium niobium oxide via mixed chloride flux growth in the presence of mesoporous silica.

A new synthesis method, "chloride flux growth in the rigid nanospace of mesoporous silica", was developed to obtain lithium niobium oxide anisotropic nanoparticles. The morphologies reflect the pore size and shape of the used mesoporous silicas. This method has great potential for synthesizing size-tuned anisotropic nanoparticles of other complex metal oxides.

Solid-State 31P Nuclear Magnetic Resonance Study of Interlayer Hydroxide Surfaces of Kaolinite Probed with an Interlayer Triethylphosphine Oxide Monolayer.

The solid acidity of the interlayer aluminol surfaces of kaolinite was explored by solid-state 31P nuclear magnetic resonance with magic angle spinning (MAS) using triethylphosphine oxide (TEPO), which formed a monolayer with a uniform orientation between the layers of kaolinite as a probe molecule. Intercalation of TEPO between the layers of kaolinite was achieved using methoxy-modified kaolinite as an intermediate. The presence of TEPO in the reaction products was revealed by the two signals at 21 and 7 ppm, which were assignable to ethyl groups in TEPO, in the solid-state 13C nuclear magnetic resonance with cross polarization and magic angle spinning techniques (13C CP/MAS NMR). The presence of TEPO between the layers of kaolinite was demonstrated by the expansion of basal spacing from 0.86 nm, the interlayer distance of methoxy-modified kaolinite to 1.16 nm, as shown by the X-ray diffraction patterns, suggesting the formation of a TEPO monolayer between the layers of kaolinite. The formation of hydrogen bonds between the P═O groups of TEPO and the aluminol groups on the interlayer surfaces of kaolinite was also revealed by the appearance of an additional OH stretching band at 3598 cm-1 in the Fourier-transform infrared spectrum and narrow solid-state 31P MAS NMR signals observed at 55-53 ppm which were shifted from the position of the physisorbed TEPO (50 ppm). These results clearly indicate that the solid acidity of interlayer aluminol groups of methoxy-modified kaolinite was probed using an interacted TEPO monolayer.

Materials Nanoarchitectonics Using 2D Layered Materials: Recent Developments in the Intercalation Process.

Layered inorganic solids as an attractive classification of 2D materials offer material diversity and a wide range of interesting properties. Layered inorganic solids provide an expandable 2D nanospace between each individual layer, the so called interlayer space, to accommodate/arrange guest species such as molecules, nanoparticles, and polymer chains and design unique nanoarchitectures, resulting in the production of intercalation compounds showing different properties in comparison to those of virgin layered materials and guest species. Layered inorganic solids can also be exfoliated to result in nanosheet production. Further ordering of exfoliated nanosheets is also possible via different methods and normally leads to creating soft materials presenting properties and applications different from that of relatively rigid intercalation compounds. Here, the latest studies and up-to-date developments on the possible techniques of designing novel types of materials using layered inorganic solids are specifically highlighted.

Interaction of Yarrowia lipolytica lipase with dithiocarbamate modified magnetic carbon Fe3O4@C-NHCS2H core-shell nanoparticles.

Fe3O4@C core-shell nanoparticles were modified by (3-aminopropyl)triethoxysilane (APTES) to generate amine functionality in the surface. Then, the amine functional groups were converted to dithiocarbamate via post-modification with carbon disulfide. This nanostructure with new functional property was used to immobilize lipase (obtained from Yarrowia lipolytica U6). Biocatalytic activity of the Fe3O4@C-NHCS-LIP was studied in this project. The interaction of lipase and support though dithiocarbamate binder was examined in the hydrolysis of p-nitrophenyl laurate. In this paper, support showed a unique feature in the immobilization of lipase by maintaining the lipase activity, raising the stability of lipase, and reusability.

Merging Cation Exchange and Photocatalytic Charge Separation Efficiency in an Anatase/K2Ti4O9 Nanobelt Heterostructure for Metal Ions Fixation.

Efficient collection and safe disposal of toxic metals ions from aqueous solutions is critical for applications in environmental remediation. Although extensive efforts have been devoted to the synthesis of functional TiO2 materials, photocatalytic reduction (photoreduction) of aqueous metal ions into solid metals remains a challenge. We designed a TiO2 nanoparticle-decorated layered titanate (K2Ti4O9) material that retained the cation exchange ability of K2Ti4O9 but also possessed the enhanced charge separation efficiency of K2Ti4O9. Combining cation exchange with enhanced charge separation efficiency results in a heterostructured material with remarkably high activity for the photoreduction of metal ions. Initially we demonstrated how the photocatalyst can efficiently reduce aqueous Ni2+ cations, whereas the benchmark TiO2-based P25 catalyst showed little to no activity. The resulting Ni-deposited heterostructure can then be used as a catalyst for visible light-induced photocatalytic H2 evolution in water.

Assembly of Hollow Carbon Nanospheres on Graphene Nanosheets and Creation of Iron-Nitrogen-Doped Porous Carbon for Oxygen Reduction.

Triblock copolymer micelles coated with melamine-formaldehyde resin were self-assembled into closely packed two-dimensional (2D) arrangements on the surface of graphene oxide sheets. Carbonizing these structures created a 2D architecture composed of reduced graphene oxide (rGO) sandwiched between two monolayers of sub-40 nm diameter hollow nitrogen-doped carbon nanospheres (N-HCNS). Electrochemical tests showed that these hybrid structures had better performance for oxygen reduction compared to physically mixed rGO and N-HCNS that were not chemically bonded together. Further impregnation of the sandwich structures with iron (Fe) species followed by carbonization yielded Fe1.6-N-HCNS/rGO-900 with a high specific surface area (968.3 m2 g-1), a high nitrogen doping (6.5 at%), and uniformly distributed Fe dopant (1.6 wt %). X-ray absorption fine structure analyses showed that most of the Fe in the nitrogen-doped carbon framework is composed of single Fe atoms each coordinated to four N atoms. The best Fe1.6-N-HCNS/rGO-900 catalyst performed better in electrocatalytic oxygen reduction than 20 wt % Pt/C catalyst in alkaline medium, with a more positive half-wave potential of 0.872 V and the same limiting current density. Bottom-up soft-patterning of regular carbon arrays on free-standing 2D surfaces should enable conductive carbon supports that boost the performance of electrocatalytic active sites.