Production of H and Glucaric Acid Using Electrocatalyst Glucose Oxidation by the Ta NiFe LDH Electrode.

The slow anodic oxygen evolution reaction (OER) significantly limits electrocatalytic water splitting for hydrogen production. We proposed the electrocatalyst for glucose oxidation by Ta-doping NiFe LDH nanosheets to simultaneously obtain glucaric acid (GRA) and hydrogen gas as a useful byproduct. Superior glucose oxidation reaction (GOR) activity is demonstrated by the optimized Ta-NiFe LDH, which has a low overpotential of 192 mV, allowing for a small Tafel slope of 70 mV dec and a current density of 50 mA cm.

Electrocatalytic Reactions for Converting CO to Value-Added Products: Recent Progress and Emerging Trends.

Carbon dioxide (CO) emissions are an important environmental issue that causes greenhouse and climate change effects on the earth. Nowadays, CO has various conversion methods to be a potential carbon resource, such as photocatalytic, electrocatalytic, and photo-electrocatalytic. CO conversion into value-added products has many advantages, including facile control of the reaction rate by adjusting the applied voltage and minimal environmental pollution.

Photoelectrochemical Epoxidation of Cyclohexene on an α-FeO Photoanode Using Water as the Oxygen Source.

This study developed a safe and sustainable route for the epoxidation of cyclohexene using water as the source of oxygen at room temperature and ambient pressure. Here, we optimized the cyclohexene concentration, volume of solvent/water (CHCN, HO), time, and potential on the photoelectrochemical (PEC) cyclohexene oxidation reaction of the α-FeO photoanode. The α-FeO photoanode epoxidized cyclohexene to cyclohexene oxide with a 72.

Development of Low-Shrink Epoxy Putty to Solve Appearance-Quality Defects of Carbon-Fiber-Reinforced Plastic Automotive Exterior Parts.

In this study, epoxy putties with novel compositions were developed for the filling of structural voids in carbon-fiber-reinforced plastics (CFRPs), which are used to fabricate automotive parts. Two constituent solutions-one consisting of epoxy resins and the other consisting of a hardener-were formulated, mixed, and then coated on CFRP surfaces, followed by curing. The surfaces were then evaluated to determine the shrinkage rates (calculated based on the liquid densities and cured mixtures), adhesion properties (determined by a peel test), and color differences (measured with a colorimeter) of the synthesized putties.

Synthesis of Waterborne Polyurethane Using Phosphorus-Modified Rigid Polyol and its Physical Properties.

In this study, a phosphorous-containing polyol (P-polyol) was synthesized and reacted with isophorone diisocyanate (IPDI) to produce water-dispersed polyurethane. To synthesize waterborne polyurethanes (WPUs), mixtures of P-polyol and polycarbonate diol (PCD) were reacted with IPDI, followed by the addition of dimethylol propionic acid, to confer hydrophilicity to the produced polyurethane. An excess amount of water was used to disperse polyurethane in water, and the terminal isocyanate groups of the resulting WPUs were capped with ethylene diamine.

Flame Retardant Submicron Particles via Surfactant-Free RAFT Emulsion Polymerization of Styrene Derivatives Containing Phosphorous.

The reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization of diethyl-(4-vinylbenzyl) phosphate (DEVBP) was performed using PEG-TTC as a macro RAFT agent. PEG-TTC (M 2000, 4000) was synthesized by the esterification of poly (ethylene glycol) methyl ether with a carboxylic-terminated RAFT agent, composed a hydrophilic poly (ethylene glycol) (PEG) block and a hydrophobic dodecyl chain. The RAFT emulsion polymerization of DEVBP was well-controlled with a narrow molecular size distribution.

Modified Epoxy Resin Synthesis from Phosphorus-Containing Polyol and Physical Changes Studies in the Synthesized Products.

Epoxy resins are commonly used to manufacture the molding compounds, reinforced plastics, coatings, or adhesives required in various industries. However, the demand for new epoxy resins has increased to satisfy diverse industrial requirements such as enhanced mechanical properties, thermal stability, or electrical properties. Therefore, in this study, we synthesized new epoxy resin (PPME) by modifying phosphorous-containing polyol.

Clarifying the mechanism of cation exchange in Ca(II)[15-MC(Cu(II)ligand)-5] complexes.

The calcium metallacrown Ca(II)[15-MC(Cu(II)N(Trpha))-5](2+) was obtained by self-assembly of Ca(II), Cu(II), and tryptophanhydroxamic acid. Its X-ray structure shows that the core calcium ion is well-encapsulated in the five oxygen cavity of the metallacrown scaffold. The kinetics of Ca-Ln core metal substitution was studied by visible spectrophotometry by addition of Ln(III) nitrate to solutions of Ca(II)[15-MC(Cu(II)N(Trpha))-5](2+) in methanol solution at pH 6.

A chemical precursor for depositing Sb2S3 onto mesoporous TiO2 layers in nonaqueous media and its application to solar cells.

Deposition of nanocrystalline Sb(2)S(3) onto a mesoporous TiO(2) photoanode is an important process in the fabrication of Sb(2)S(3)-sensitized solar cells. In order to generate oxide-free nanosized Sb(2)S(3), a single-source precursor for the chemical bath deposition of Sb(2)S(3) in nonaqueous media, Sb(III)(thioacetamide)(2)Cl(3), was synthesized and used to produce high-quality Sb(2)S(3) for solar cells.

Panchromatic photon-harvesting by hole-conducting materials in inorganic-organic heterojunction sensitized-solar cell through the formation of nanostructured electron channels.

Additional photon-harvesting by hole transporting materials in Sb(2)S(3)-sensitized solar cell is demonstrated through the formation of electron channels in the hole transporter such as P3HT (poly(3-hexylthiophene)) and PCPDTBT(poly(2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)) that can act as both a hole conductor and light absorber. As a result, the short-circuit current density is improved with an increment in overall efficiency. These findings provide new insights into use of light-absorbing conjugated polymers as a hole conductor in the inorganic-organic heterojunction sensitized solar cells.

Enhancing the device performance of Sb2S3-sensitized heterojunction solar cells by embedding Au nanoparticles in the hole-conducting polymer layer.

Performance of Sb(2)S(3)-sensitized heterojunction solar cells is enhanced by embedding Au nanoparticles in the poly-3-hexylthiophene (P3HT) hole-conducting polymer layer. The improved charge transfer/transport at the Sb(2)S(3)/P3HT/Au interface by extended interface area of the P3HT/Au counter electrode and the re-absorption of the backscattering light from the embedded Au nanoparticles enhanced the device performance: J(sc) 11.0 to 12.

Influencing the size and anion selectivity of dimeric Ln(3+)[15-metallacrown-5] compartments through systematic variation of the host side chains and central metal.

Dimeric Ln(3+)[15-metallacrown-5] compartments selectively recognize carboxylates through guest binding to host metal ions and intermolecular interactions with the phenyl side chains. A systematic study is presented on how the size, selectivity, and number of encapsulated guests in the dimeric containers is influenced by the Ln(3+)[15-metallacrown(Cu(II))-5] ligand side chain and central metal. Compartments of varying heights were assembled from metallacrowns with S-phenylglycine hydroxamic acid (pgHA), S-phenylalanine hydroxamic acid (pheHA), and S-homophenylalanine hydroxamic acid (hpheHA) ligands.

Improvement of external quantum efficiency depressed by visible light-absorbing hole transport material in solid-state semiconductor-sensitized heterojunction solar cells.

A mesoporous (mp)-TiO(2)/Sb(2)S(3)/P3HT [poly(3-hexylthiophene)] heterojunction solar cell displays reduced external quantum efficiency (EQE) at a wavelength of approximately 650 nm. This loss in EQE is due to incomplete charge carrier transport because the transportation of charge carriers generated in P3HT by the absorption of light into Sb(2)S(3) was inefficient, and consequently, the carriers recombined. The depression of the EQE was greatly relieved by introducing the porous structure formed by thermal decomposition of 2,2'-azobisisobutyronitrile (AIBN) into the P3HT layer.

Toward interaction of sensitizer and functional moieties in hole-transporting materials for efficient semiconductor-sensitized solar cells.

Sb(2)S(3)-sensitized mesoporous-TiO(2) solar cells using several conjugated polymers as hole-transporting materials (HTMs) are fabricated. We found that the cell performance was strongly correlated with the chemical interaction at the interface of Sb(2)S(3) as sensitizer and the HTMs through the thiophene moieties, which led to a higher fill factor (FF), open-circuit voltage (V(oc)), and short-circuit current density (J(sc)). With the application of PCPDTBT (poly(2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)) as a HTM in a Sb(2)S(3)-sensitized solar cell, overall power conversion efficiencies of 6.

Effects of the central lanthanide ion crystal radius on the 15-MC(Cu(II)(N)pheHA)-5 structure.

Twenty crystal structures of the Ln(III)[15-MC(CuII(N)pheHA)-5](3+) complex, where pheHA = phenylalanine hydroxamic acid and where Ln(III) = Y(III) and La(III)-Tm(III), except Pm(III), with the nitrate and/or hydroxide anion are used to assess the effect of the central metal ion on the metallacrown structure. Each Ln(III)[15-MC(CuII(N)pheHA)-5](3+) complex is amphiphilic with a hydrophobic side consisting of the phenyl groups of the pheHA ligand and a side without the aromatic residues. Three general structures are observed for the Ln(III)[15-MC(CuII(N)pheHA)-5](3+) complexes.

Gd(III)[15-metallacrown-5] recognition of chiral α-amino acid analogues.

Chiral Ln(III)[15-metallacrown-5] complexes with phenyl side chains have been shown to encapsulate aromatic carboxylates reversibly in their hydrophobic cavities. Given the importance of selective guest binding for applications of supramolecular containers in synthesis, separations, and materials design, the affinity of Gd(III)[15-metallacrown(Cu(II), L-pheHA)-5] hosts for a series of chiral carboxylate guests with varying substitutions on the α-carbon (phenylalanine, N-acetyl-phenylalanine, phenyllactate, mandelate, methoxyphenylacetate) has been investigated. Differential binding of S- and R-phenylalanine was revealed by X-ray crystallography, as the S-enantiomer exclusively forms associative hydrogen bonds with oxygen atoms in the metallacrown ring.

Metal-dependent phase selection in coordination polymers derived from a C(2V)-symmetric tricarboxylate.

Reacting biphenyl-3,4',5-tricarboxylic acid (H(3)BHTC) with the appropriate metal salt yields the microporous coordination polymers (MCPs) Mn(3)(BHTC)(2) (1), Mg(3)(BHTC)(2) (2), and Co(3)(BHTC)(2) (3) containing hourglass metal clusters. The addition of Cu to reactions with Co(II), Fe(III), or Mn(II) leads to the formation of heterobimetallic UMCM-150 isostructural analogues Co(1)Cu(2)(BHTC)(2) (4), Fe(1)Cu(2)(BHTC)(2) (5), and Mn(1)Cu(2)(BHTC)(2) (6) containing both paddlewheel and trinuclear metal clusters. X-ray diffraction analysis of the crystals of the heterobimetallic MCPs suggests that Cu on the trinuclear site of UMCM-150 was replaced by the other metal, whereas Cu in paddlewheel sites remains unchanged.

Thermodynamics of core metal replacement and self-assembly of Ca(2+) 15-metallacrown-5.

The equilibria for core Ca(2+) replacement by Ln(3+) in copper(II) 15-MC-5 complexes have been investigated using a series of visible spectrophotometric titrations of calcium(II) metallacrowns ({Ca(II)[15-MC(Cu(II)(N)(L))-5]}(2+)) with Ln(3+) ions (H(2)L = pheha, (S)-alpha-phenylalaninehydroxamic acid, or trpha, (S)-alpha-tryptophanhydroxamic acid). These studies allowed the determination of the equilibrium constants for the reaction {Ca(II)[15-MC(Cu(II)(N)(L))-5]}(2+) + Ln(3+) --> {Ln(III)[15-MC(Cu(II)(N)(L))-5]}(3+) + Ca(2+) in methanol/water 9:1 (Ln(3+) = La(3+), Gd(3+), Dy(3+), Er(3+)) or 99:1 (Ln(3+) = La(3+), Nd(3+), Gd(3+), Dy(3+), Er(3+), Yb(3+)), respectively. The log K for these reactions decreases with increasing atomic number of the lanthanide(III), ranging from 6.

Establishing the binding affinity of organic carboxylates to 15-metallacrown-5 complexes.

The reaction of L-phenylalanine hydroxamic acid (H(2)L-pheHA) with copper(II) and lanthanide(III) salts yields 15-Metallacrown-5 structures of the general composition Ln(X)n[Cu(II)(L-pheHA)](5)((3-n)+) where X can represent a wide variety of anions. With five copper ions and one central lanthanide ion, the Ln[15-MC-5] complexes have multiple positions where these anionic guests may bind to the metallacrown host. In addition, these metallacrowns are amphiphilic, containing one face that is primarily hydrophobic (due to the five benzyl side chains which are oriented upon the same face of the molecule) and a face that is hydrophilic which has no impediment to solvent access.