The one-pot catalytic conversion of cellulose into ethylene glycol (EG) is an attractive way of biomass utilization. However, low-cost, efficient, and stable catalysts are the premise and research challenges of industrial application. Herein, the magnetic recyclable W–Ni@C catalyst was synthesized by in-situ pyrolysis of Ni-MOFs impregnated with ammonium metatungstate. Compared with the Ni-W bimetallic catalysts prepared by the impregnation method and the sol–gel method, the W–Ni@C catalyst for cellulose hydrogenolysis reaction can achieve a higher ethylene glycol yield (67.1% vs 43.3% and 42.6%) and 100% of cellulose conversion rate. The uniformly dispersed Ni nanoparticles and abundant defective WOx were formed in a reductive atmosphere generated in pyrolysis of Ni-MOFs, which was indispensable for the hydrogenolysis of cellulose into EG. Besides, the hierarchical porous carbon derived from organic ligands in Ni-MOFs reduces the mass transfer resistance while confining Ni nanoparticles and WOx to prevent their leaching, effectively enhancing the stability of the W–Ni@C catalyst. Therefore, the remarkable catalytic performance, the simple and effective recovery method as well as satisfying stability would make W–Ni@C become a promising catalyst for the conversion of cellulose to EG.
Four 1,5-diphenyl-3-aromatic heterocyclyl-2-pyrazoline-based sulfonium salt photoacid generators (PAGs) with different aromatic heterocycles substituted on C3 atom and dimethyl sulfonium group on C5 atom were synthesized. These PAGs were highly photosensitive in the 365–425 nm light-emitting diode region, and the intramolecular charge transfer from the pyrazoline ring to sulfonium salts induced efficient photolysis and high ΦH+. The heterocycles as well as their substituted positions significantly influenced the energy of the S2 orbital, which was determined by the electrochemical and absorption properties of the PAGs. The raising of the S2 orbital energy enlarged the energy gap of S0–S2 and S1–S2, resulting in blue shift of the absorption spectra and increase in the quantum yield of photoacid generation (ΦH+), respectively. When the energy of excited electrons was higher than that of the S2 orbital, the transition from S0 to S2 (π–π*) occurred before the C-S cleavage on S1 and the PAGs showed high ΦH+ values (0.52–0.72). The transition from S0 to S1 (π–σ*) occurred when the energy of electrons is lower than that of the S2 orbital, and the PAGs showed low ΦH+ value. The photopolymerization kinetics demonstrated that these PAGs were highly efficient cationic photoinitiators. 相似文献
Trimethylamine N-oxide (TMAO), as a gut-derived metabolite, has been found to be associated with enhanced risk for atherosclerosis and cardiovascular disease. We presented a method for targeted profiling of TMAO and betaine in serum and food samples based on a combination of one-step sample pretreatment and proton nuclear magnetic resonance spectroscopy. The key step included a processing of sample preparation using a selective solid-phase extraction column for retention of basic metabolites. Proton signals at δ 3.29 and δ 3.28 were employed to quantify TMAO and betaine, respectively. The developed method was examined with acceptable linear relationship, precision, stability, repeatability, and accuracy. It was successfully applied to detect serum levels of TMAO and betaine in TMAO-fed mice and high-fructose-fed rats and also used to determine the contents of TMAO and betaine in several kinds of food, such as fish, pork, milk, and egg yolk. 相似文献
Science China Chemistry - Extracting photogenerated species from bulk to surface is an essential process for gaining efficient semiconductor-based photocatalysis. However, compared with charged... 相似文献
Transition metal catalysed C−H bond activation chemistry has emerged as an exciting and promising approach in organic synthesis. This allows us to synthesize a wider range of functional molecules and conjugated polymers in a more convenient and more atom economical way. The formation of C−C bonds in the construction of pi-conjugated systems, particularly for conjugated polymers, has benefited much from the advances in C−H bond activation chemistry. Compared to conventional transition-metal catalysed cross-coupling polymerization such as Suzuki and Stille cross-coupling, pre-functionalization of aromatic monomers, such as halogenation, borylation and stannylation, is no longer required for direct arylation polymerization (DArP), which involve C−H/C−X cross-coupling, and oxidative direct arylation polymerization (Ox-DArP), which involves C−H/C−H cross-coupling protocols driven by the activation of monomers’ C(sp2)−H bonds. Furthermore, poly(annulation) via C−H bond activation chemistry leads to the formation of unique pi-conjugated moieties as part of the polymeric backbone. This review thus summarises advances to date in the synthesis of conjugated polymers utilizing transition metal catalysed C−H bond activation chemistry. A variety of conjugated polymers via DArP including poly(thiophene), thieno[3,4-c]pyrrole-4,6-dione)-containing, fluorenyl-containing, benzothiadiazole-containing and diketopyrrolopyrrole-containing copolymers, were summarized. Conjugated polymers obtained through Ox-DArP were outlined and compared. Furthermore, poly(annulation) using transition metal catalysed C−H bond activation chemistry was also reviewed. In the last part of this review, difficulties and perspective to make use of transition metal catalysed C−H activation polymerization to prepare conjugated polymers were discussed and commented. 相似文献
Journal of Inclusion Phenomena and Macrocyclic Chemistry - Poly(ethylene glycol) diamine 1,1’-disubstituted ferrocene was utilized as a size-com-plementary site to synthesize lower coverage... 相似文献
Perovskite is a promising non-noble catalyst and has been widely investigated for the electrochemical oxygen evolution reaction (OER). However, there is still serious lack of valid approaches to further enhance their catalytic performance. Herein, we propose a spin state modulation strategy to improve the OER electrocatalytic activity of typical perovskite material of LaCoO3. Specifically, the electronic configuration transition was realized by a simple high temperature thermal reduction process. M-H hysteresis loop results reveal that the reduction treatment can produce more unpaired electrons in 3d orbit by promoting the electron transitions of Co from low spin state to high spin state, and thus lead to the increase of the spin polarization. Electrochemical measurements show that the catalytic performance of LaCoO3 is strongly dependent on its electronic configuration. With the optimized reduction treatment, the overpotential for the OER process in 0.5 M KOH electrolyte solution at 10 mA cm−2 current density was 396 mV, significantly lower than that of the original state. Furthermore, it can mediate efficient OER with an overpotential of 383 mV under an external magnetic field, which is attributed to the appropriate electron filling. Our results show that electron spin state regulation is a new way to boost the OER electrocatalytic activity. 相似文献
A new class of ruthenium(II) polypyridine complexes with a series of D–π–A–π–D type (D=donor, A=acceptor) ligands was synthesized and characterized by 1H NMR spectroscopy, mass spectrometry, and elemental analysis. The photophysical and electrochemical properties of the complexes were also investigated. The newly synthesized ruthenium(II) polypyridine complexes were found to exhibit two intense absorption bands at both high‐energy (λ=333–369 nm) and low‐energy (λ=520–535 nm) regions. They are assigned as intraligand (IL) π→π* transitions of the bipyridine (bpy) and π‐conjugated bpy ligands, and IL charge‐transfer (CT) transitions from the donor to the acceptor moiety with mixing of dπ(RuII)→π*(bpy) and dπ(RuII)→π*(L) MLCT characters, respectively. In addition, all complexes were demonstrated to exhibit intense red emissions at approximately λ=727–744 nm in degassed dichloromethane at 298 K or in n‐butyronitrile glass at 77 K. Nanosecond transient absorption (TA) spectroscopy has also been carried out, establishing the presence of the charge‐separated state. In order to understand the electrochemical properties of the complexes, cyclic voltammetry has also been performed. Two quasi‐reversible oxidation couples and three quasi‐reversible reduction couples were observed. One of the ruthenium(II) complexes has been utilized in the fabrication of memory devices, in which an ON/OFF current ratio of over 104 was obtained. 相似文献