Solar-Driven CO2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

Photothermal CO₂ reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium-modified carbon-supported cobalt (K⁺−Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus-pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K⁺−Co−C catalyst shows a record-high photothermal CO₂ hydrogenation rate of 758 mmol g_cat⁻¹ h⁻¹ (2871 mmol g_Co⁻¹ h⁻¹) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO₂ reduction reactions. We further demonstrate with this catalyst effective CO₂ conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.     

The role of copper(II) ions in the oxidation of 5-hydroxy-6-methyluracil in the ground and electronically excited states with molecular oxygen in aqueous solutions

A spectral fluorescence study of photoinduced reactions in aqueous solutions has been carried out in order to examine the mechanisms of the oxidation of 5-hydroxy-6-methyluracil (I) in the ground and electronically excited states by molecular oxygen in the presence of copper(II) chloride. It has been found that 5,5,6-trihydroxy-6-methylpyrimidine-2,4-dione (II) is formed upon the photolysis of I. The spectral parameters (λ_max) and the quantum yields (φ) of fluorescence (FL) of compounds I (φ = 8 × 10^–4; λ_max = 362 nm) and II (φ = 17 × 10^–4; λ_max = 306, 330 nm) have been determined. A reaction scheme was proposed, according to which the photooxidation of I occurs through the steps of the generation of the radical cation I ^?+ and the superoxide anion О ₂ ^?- with the subsequent formation of 5,5,6-trihydroxy-6-methylpyrimidine-2,4-dione. The catalytic and inhibitory effects of Cu(II) ions on the oxidation of 5-hydroxy-6-methyluracil in the ground and electronically excited states, respectively, by the oxygen radical anion О ₂ ^?- have been revealed.     

Synthesis of gold nanoparticles and thin films with the use of micellar solution of Brij 30

Gold nanoparticles (NPs) with the average core diameter d _Au = 6.8 ± 1.6 nm have been synthesized in reverse micelles of the oxyethylated surfactant Brij 30. It has been shown that thin NP films can be produced directly from a micellar solution with the use of glass substrates functionalized with aminosilane. Synthesis of NPs and film formation have been studied by UV-Vis spectroscopy, photon correlation spectroscopy, X-ray diffraction, TEM, SEM, and AFM.     

Synthesis of difunctional 1,4-dimethyl-1,4-disilacyclohexanes

Transformations of HVinSiCl₂, HVinSi(Me)Cl, HVinSi(Me)Ph, and HVinSi(Me)NEt₂ in the presence of Pt catalyst were studied. In dilute solutions, the reaction gave a mixture of structural and stereoisomers of five- and six-membered disilacyclanes, resulting from intramolecular cyclization of the initially formed linear dimer. In the case of methyl(phenyl)disilacyclane, the structural isomers were separated andtrans-1,4-dimethyl-1,4-diphenyl-1,4-disilacyclohexane was isolated. The reaction of this product with HCl in the presence of AlCl₃ followed by hydrolysis resulted in the synthesis oftrans-1,4-dichloro- andtrans-1,4-dihydroxy-1,4-dimethyl-1,4-disilacyclohexanes. The structures of the structural and stereoisomers synthesized were confirmed by¹H,¹³C, and²⁹Si NMR and IR spectroscopies and mass spectrometry. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1734–1738, September, 1999.     

Electron diffraction and quantum chemical study of the molecular structure of 4-methylbenzene sulfochloride

A combined electron diffraction and mass spectrometric study was carried out to investigate the molecular structure of 4-methylbenzene sulfochloride at 330(2) K. An analysis of the electron diffraction data was performed in terms of the r_α structure. Several models of geometrical structure having different orientations of the sulfochloride group relative to the plane of the benzene ring are treated. The following values of structural parameters were obtained: r_α(C-H)_meth= 1.104(41)Å, r_a(C-H)/_phen = 1.103(27)Å, r_a(C-C)_phen = 1.403(7) Å, r_a(C-C)_meth = 1.512(25) Å, r_a(C-S) =1.758(6) Å, r_a(S = O) = 1.419(3) Å,r _a(S-Cl) = 2.049(5) Å, ∠CCH_meth = 106.9(47)?, ∠CSO = 110.5(6)?, ∠CSCl = 101.3(6)°, ∠OSO = 120.5(9)°. The angle between the plane of the benzene ring and the plane of the S-Cl bond was found to be 83°. Ab initio and semiempirical quantum chemical calculations were accomplished to estimate the geometrical and energy parameters and compare them with electron diffraction data.     

An Investigation of the Positive Column of a Cd–Ne Glow Discharge: II. Afterglow

The afterglow of a Cd–Ne glow discharge is investigated theoretically and experimentally. The time-dependent electron Boltzmann equation and the balance equations for the Cd excited states and charged particles have been self-consistently solved. The temporal relaxation of the electron energy distribution function, electron, and cadmium excited states densities is reported and the influence of neon and cadmium vapor pressure on the plasma characteristics in the afterglow is studied. The modeling compares favorably with experimental results.     

Synthesis of 5-Phenyl-7-trifluoromethyl-2,3-dihydroimidazo[1,2-a]pyridines

Syntheses are reported for a series of 2-alkylamino-6-phenyl-4-trifluoromethylpyridines. The reaction of 3-cyano-2-(hydroxyalkylamino)-6-phenyl-4-trifluoromethylpyridines with thionyl chloride gave the corresponding 2-(chloroalkylamino)pyridines, 8-cyano-5-phenyl-7-trifluoromethyl-2,3-dihydro-imidazo[1,2-a]pyridines, and 9-cyano-6-phenyl-8-trifluoromethyl-2,3,4-trihydropyrido[1,2-a]-pyrimidines. X-ray diffraction structural analysis was used to study 8-cyano-5-phenyl-7-trifluoromethyl-2,3-dihydroimidazo[1,2-a]pyridine.     

Instance-optimality in probability with an -minimization decoder

Let Φ(ω), ωΩ, be a family of n×N random matrices whose entries _i,j are independent realizations of a symmetric, real random variable η with expectation and variance . Such matrices are used in compressed sensing to encode a vector by y=Φx. The information y holds about x is extracted by using a decoder . The most prominent decoder is the ℓ₁-minimization decoder Δ which gives for a given the element which has minimal ℓ₁-norm among all with Φz=y. This paper is interested in properties of the random family Φ(ω) which guarantee that the vector will with high probability approximate x in to an accuracy comparable with the best k-term error of approximation in for the range kan/log₂(N/n). This means that for the above range of k, for each signal , the vector satisfies

with high probability on the draw of Φ. Here, Σ_k consists of all vectors with at most k nonzero coordinates. The first result of this type was proved by Wojtaszczyk [P. Wojtaszczyk, Stability and instance optimality for Gaussian measurements in compressed sensing, Found. Comput. Math., in press] who showed this property when η is a normalized Gaussian random variable. We extend this property to more general random variables, including the particular case where η is the Bernoulli random variable which takes the values with equal probability. The proofs of our results use geometric mapping properties of such random matrices some of which were recently obtained in [A. Litvak, A. Pajor, M. Rudelson, N. Tomczak-Jaegermann, Smallest singular value of random matrices and geometry of random polytopes, Adv. Math. 195 (2005) 491–523].