Yixing Luo,Qifeng Yang,Wendan Nie,Qilu Yao,Zhujun Zhang,Zhang-Hui Lu
Hydrogen (H2), a regenerable and promising energy carrier, acts as an essential role in the construction of a sustainable energy system. Formic acid (HCOOH, FA), a natural biological metabolic products and also accessible through carbon dioxide (CO2) reduction, has a great potential to serve as a prospective H2 supplier for the fuel cell. Herein, ultrafine and electron-rich IrPdAu alloy nanoparticles with a size of 1.4 nm are highly dispersed on amine-modified mesoporous SiO2 (NH2-SBA-15) and used as a highly active and selective catalyst for fast H2 production from FA. The as-synthesized IrPdAu/NH2-SBA-15 possesses superior catalytic activity and 100% H2 selectivity with initial turnover frequency values of 6316 h–1 with the additive of sodium formate (SF) and 4737 h–1 even without SF at 298 K, comparable to the most effective heterogeneous catalysts ever published. The excellent performance of IrPdAu/NH2-SBA-15 was not only ascribed to the combination of the electronic synergistic effect of trimetallic alloys and the strong metal–support interaction effect but also attributed to the amine (−NH2) alkaline groups grafted on SBA-15, which is beneficial to boost the split of the O–H bond of FA.
Background Sugar phosphates (SPx) play important role in the metabolism of the organism. SPx such as glycerate 3-phosphate, fructose 6-phosphate and glucose 6-phosphate in biological samples have the poor stability, similar structure and low abundance, which make their separation and detection more challenging. Method UiO-66-NH 2 and ZrO 2 coated SiO 2 (SBA-15) hard-core–shell adsorbents (UiO-66-NH 2 @SBA-15 and ZrO 2 @SBA-15) were synthesized, which were further used for dispersive solid-phase extraction for enriching the SPx in biological samples. The protocol was developed by UiO-66-NH 2 @SBA-15 and ZrO 2 @SBA-15 coupled with gas chromatography-mass spectrometry for the detection of trace SPx. The univariate experiment and response surface methodology were used to optimize the adsorption and desorption conditions. Results The adsorbents showed excellent adsorption capacity and specificity towards SPx, which were proved by adsorption and selective experiments. Under the optimized conditions, there were good linearity within the range of 5.0–5000.0 ng mL −1 , low limits of detection (0.001–1.0 ng mL −1 ), low limits of quantification (0.005–5.0 ng mL −1 ) and good precision (relative standard deviation less than 14.7 % for intra-day and inter-day). The satisfactory recoveries (89.1–113.8 %) and precision (0.5–14.6 %) were obtained when the sorbents were used to extract SPx from serum, saliva and cell samples. Moreover, UiO-66-NH 2 @SBA-15 was applied to the quantitative analysis of SPx from gastric cancer patients, because of a higher adsorption capacity (169.5–196.1 mg g −1 ). Conclusions UiO-66-NH 2 @SBA-15 showed great potential in the extraction of SPx in biological samples, which was beneficial to find out the metabolic change of SPx and explain the pathogenesis of the disease.
Qian-Wen Lu,Qing He,Qing-Shuai Zhang,Da Sheng,Song-Hai Wu,Yong Liu,Xu Han
Although thermocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-formylfuran (DFF) by O2 is an important reaction, achieving a high yield of DFF is still challenging. In this study, a series of MoxCuy/NH2-SBA-15 are prepared, and Mo3Cu1/NH2-SBA-15 exhibits the desirable catalytic reactivity with a complete conversion of HMF and high selectivity of 94.4% toward DFF. XPS and EPR analyses indicate that the abundant oxygen vacancies (Ov) and Cu(I) are the reactive sites for O2 activation. Quenching experiments and various characterizations reveal that superoxo (≡Cu(II)/Ov-OO•) on the surface of catalyst, instead of •OH and O2•–, are the primary oxidizing species to abstract H from HMF to RCH2-O•, accompanied by the formation of ≡Cu(II)/Ov-OOH peroxo. Meanwhile, the doped Mo(V/VI) further activates ≡Cu(II)/Ov-OOH peroxo to form ≡Mo-(η2-O2) peroxo, which significantly promotes the oxidation selectivity of RCH2-O• toward DFF via the H-abstraction pathway. This study provides new insight on selective thermal-oxidation of biomass-derived compounds to high-value-added chemicals via regulating reactive oxidizing species on the surface of catalysts.
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