Catalytic Fast Pyrolysis of Soybean Straw Biomass for Glycolaldehyde-Rich Bio-oil Production and Subsequent Extraction.

In this study, soybean straw (SS) as a promising source of glycolaldehyde-rich bio-oil production and extraction was investigated. Proximate and ultimate analysis of SS was performed to examine the feasibility and suitability of SS for thermochemical conversion design. The effect of the co-catalyst (CaCl2 + ash) on glycolaldehyde concentration (%) was examined. Thermogravimetric-Fourier-transform infrared (TG-FTIR) analysis was applied to optimize the pyrolysis temperature and biomass-to-catalyst ratio for glycolaldehyde-rich bio-oil production. By TG-FTIR analysis, the highest glycolaldehyde concentration of 8.57% was obtained at 500 °C without the catalyst, while 12.76 and 13.56% were obtained with the catalyst at 500 °C for a 1:6 ratio of SS-to-CaCl2 and a 1:4 ratio of SS-to-ash, respectively. Meanwhile, the highest glycolaldehyde concentrations (%) determined by gas chromatography-mass spectrometry (GC-MS) analysis for bio-oils produced at 500 °C (without the catalyst), a 1:6 ratio of SS-to-CaCl2, and a 1:4 ratio of SS-to-ash were found to be 11.3, 17.1, and 16.8%, respectively. These outcomes were fully consistent with the TG-FTIR results. Moreover, the effect of temperature on product distribution was investigated, and the highest bio-oil yield was achieved at 500 °C as 56.1%. This research work aims to develop an environment-friendly extraction technique involving aqueous-based imitation for glycolaldehyde extraction with 23.6% yield. Meanwhile, proton nuclear magnetic resonance (1H NMR) analysis was used to confirm the purity of the extracted glycolaldehyde, which was found as 91%.

Homogeneous Molecular Iron Catalysts for Direct Photocatalytic Conversion of Formic Acid to Syngas (CO+H2 ).

The catalytic decomposition of formic acid to generate syngas (a mixture of H2 and CO) is a highly valuable strategy for energy conversion. Syngas can be used directly in internal combustion engines or can be converted to liquid fuels, meeting future energy challenges in a sustainable manner. Herein, we report the use of homogeneous molecular iron catalysts combined with a CdS nanorods (NRs) semiconductor to construct a highly efficient photocatalytic system for direct conversion of formic acid to syngas at room temperature and atmospheric pressure. Under optimal conditions, the photocatalytic system presents an activity of 150 mmol gcatalyst -1 h-1 towards H2 , and an apparent quantum yield (AQY) of 16.8 %, making it among the most active noble-metal-free photocatalytic systems for H2 evolution from formic acid under visible light. Meanwhile, these iron-based molecular catalysts also demonstrate remarkable enhancement in CO evolution with robust stability. The mechanistic role of the molecular catalyst is further investigated by using cyclic voltammetry, which suggests the formation of FeI species as the key step in the catalytic conversion of formic acid to syngas.

Enhanced photocatalytic H2 production under visible light on composite photocatalyst (CdS/NiSe nanorods) synthesized in aqueous solution.

Cocatalysts play a critical role in the activity and stability of photocatalytic systems. Currently, efficient cocatalysts mainly comprise of expensive noble metals. Herein we report a composite photocatalyst consisting of CdS nanorods (NRs) and noble-metal-free cocatalyst NiSe, which efficiently enhances the hydrogen production activity of CdS NRs under visible light. NiSe was synthesized through a facile aqueous solution method and CdS/NiSe NRs composites were prepared by in situ deposition of NiSe on CdS NRs. This provides increased contact between cocatalyst and photosensitizer leading to enhanced electron transfer at the interface of NiSe and CdS. The current photocatalytic system gave the highest hydrogen evolution rate of 340 µmol h-1 under optimal conditions. The enhanced stability of the system was observed for 30 h of irradiation resulting in 14 mmol of hydrogen evolution. The highest AQY of 12% was observed using the 420 nm monochromatic light. In addition, CdS/NiSe NRs showed significant higher H2 evolution rate than that of 1.0 wt% loaded CdS/Pt NRs proving NiSe as highly efficient cocatalyst. Photoluminescence spectra and the photocurrent response were used to confirm the efficient charge transfer at the interface of NiSe and CdS nanorods. The work presented here demonstrates the successful use of an inexpensive, non-noble-metal cocatalyst for enhanced photocatalytic hydrogen production.

Synergistic Effect of a Molecular Cocatalyst and a Heterojunction in a 1 D Semiconductor Photocatalyst for Robust and Highly Efficient Solar Hydrogen Production.

Photocatalytic production of hydrogen by water splitting is a promising pathway for the conversion of solar energy into chemical energy. However, the photocatalytic conversion efficiency is often limited by the sluggish transfer of the photogenerated charge carriers, charge recombination, and subsequent slow catalytic reactions. Herein, we report a highly active noble-metal-free photocatalytic system for hydrogen production in water. The system contains a water-soluble nickel complex as a molecular cocatalyst and zinc sulfide on 1D cadmium sulfide as the heterojunction photocatalyst. The complex can efficiently transport photogenerated electrons and holes over a heterojunction photocatalyst to hamper charge recombination, leading to highly improved catalytic efficiency and durability of a heterojunction photocatalyst- molecular cocatalyst system. The results show that under optimal conditions, the average apparent quantum yield was approximately 58.3 % after 7 h of irradiation with monochromatic 420 nm light. In contrast, the value is only 16.8 % if the molecular cocatalyst is absent. Such a remarkable performance in a molecular cocatalyst-based photocatalytic system without any noble metal loading has, to the best of our knowledge, not been reported to date.

Enhanced photocatalytic H2 production on CdS nanorods with simple molecular bidentate cobalt complexes as cocatalysts under visible light.

Photocatalytic hydrogen production via water splitting has attracted much attention for future clean energy application. Herein we report a noble-metal-free photocatalytic hydrogen production system containing a simple bidentate cobalt Schiff base complex as the molecular cocatalyst, CdS nanorods as the photosensitizer, and ascorbic acid as the electron donor. The system shows highly enhanced photocatalytic activity compared to pure CdS NRs under visible light (λ > 420 nm). Under optimal conditions, the turnover numbers (TONs) for hydrogen production reached ∼15 200 after 12 hours of irradiation, and an apparent quantum yield of ∼27% was achieved at 420 nm monochromatic light. Steady-state photoluminescence (PL) spectra indicated efficient charge transfer between the excited CdS NRs and the cobalt cocatalyst for improved hydrogen production. Spectroscopic studies of the photocatalytic reaction revealed the reduction of the Co(ii) complex to Co(i) species, which are probably active intermediates for hydrogen evolution. On the basis of the spectroscopic studies, we propose a reaction mechanism for hydrogen production in the present photocatalytic system.

5-Hy-droxy-2-{(E)-[(3-nitro-phen-yl)iminio]meth-yl}phenolate.

The title compound, C(13)H(10)N(2)O(4), crystallized as the zwitterionic tautomer. As a result, the phenolate C-O(-) bond [1.296 (2) Å] is shorter than a normal Csp(2)-O(H) bond, and the azomethine C=N bond [1.314 (2) Å] is longer than a normal C=N double bond. The mol-ecule is nearly planar, the mean plane of the nitro-substituted benzene ring forming dihedral angles of 9.83 (7) and 8.45 (9)° with the other benzene ring and with the nitro group, respectively. The mol-ecular conformation is stabilized by an intra-molecular N-H⋯O hydrogen bond. In the crystal, strong O-H⋯O hydrogen bonds link the mol-ecules into double-stranded chains along the b-axis direction. Within the chains there are π-π interactions involving the benzene rings of adjacent molecules [centroid-centroid distance = 3.669 (1) Å]. The chains are linked via C-H⋯O hydrogen bonds, forming R(2) (1)(6), R(2) (1)(7) and R(2) (2)(10) ring motifs.

2-[(E)-N-(Adamantan-1-yl)carbox-imidoyl]-6-eth-oxy-phenol.

In the title compound, C(19)H(25)NO(2), the 3-eth-oxy-2-hy-droxy-benzaldehyde group is almost planar (r.m.s. deviation = 0.029 Å). An intra-molecular O-H⋯N hydrogen bond generates an S(6) ring. There are no inter-molecular hydrogen bonds.

2-Eth-oxy-6-{(E)-[(4-methyl-phen-yl)imino]-meth-yl}phenol.

The asymmetric unit of the title compound, C(16)H(17)NO(2), contains two mol-ecules in which the dihedral angles between the 3-eth-oxy-2-hy-droxy-benzaldehyde and toluidine moieties are 16.87 (8) and 19.93 (6)°. S(6) rings are present in both mol-ecules due to intra-molecular O-H⋯N hydrogen bonds. In the crystal, one of the mol-ecules is dimerized with an inversion-generated partner, due to two C-H⋯O inter-actions. This generates an R(2) (2)(8) loop.