Ultra-fine Pd nanoparticles confined in a porous organic polymer: A leaching-and-aggregation-resistant catalyst for the efficient reduction of nitroarenes by NaBH4.

Porous organic polymers (POPs) containing nitrogenous substituents have potential practical applications as heterogeneous catalysts based upon controlled porous structure and surface-anchored noble metal nanoparticles (NMNPs). In this work we prepared a POP material from piperazine and cyanuric chloride starting materials (PC-POP). The PC-POP material contains numerous triazinyl moieties, thus rendering the pores hydrophobic. Subsequently, by means of a novel reverse double-solvent approach (RDSA), microdroplets of Pd(AcO)2/CH2Cl2 were introduced into the hydrophobic pores of PC-POP in an aqueous environment; Pd(II) was rapidly reduced by NaBH4 to form ultra-fine Pd NPs and confined within the pores of PC-POP at high dispersity. The extensive porosity and dispersity of the Pd NPs made the active sites readily accessible, and led to efficient mass transfer. Thus, Pd@PC-POP exhibits superior catalytic performance in catalytic reduction of various nitroarenes. Furthermore, Pd@PC-POP has excellent recyclability, without significant loss of activity nor leaching of Pd active sites during 10 successive reaction cycles. This work points to a practical and cost-effective approach to preparation of POP materials, and also for confining ultra-fine NMNPs in POPs for use as catalysts.

Hollow mesoporous silica nanotubes modified with palladium nanoparticles for environmental catalytic applications.

Nowadays, chemical catalytic methods for the treatment of organic wastes are attracting more and more research attention. In the current research, novel catalysts with palladium nanoparticles (Pd NPs) supported on the hollow mesoporous silica nanotubes (h-mSiO2) were synthesized for the catalytic reduction of 4-nitrophenol (4-NP) and hydrodechlorination (HDC) of 4-chlorophenol (4-CP). The key point for the fabrication of the catalysts is that a certain thickness of the silica shell was wrapped on the multiwalled carbon nanotubes (MWNTs) or Pd/MWNTs through biphase stratification approach, and then the samples were calcined to remove the MWNTs. Thereby, h-mSiO2 and Pd@h-mSiO2 samples were obtained. The prepared materials have excellent pore structure and exhibit high specific surface areas. The reduction of 4-NP by the Pd/h-mSiO2 and Pd@h-mSiO2 catalysts showed higher TOF values than many other catalysts, and the yield of HDC of 4-CP to phenol reached 100% with a low loading of Pd in water solvent. The excellent catalytic activities of the Pd/h-mSiO2 and Pd@h-mSiO2 catalysts should attribute to the excellent connectivity of the h-mSiO2 which not only can increase the accessibility of the Pd active sites but also enhance the mass transfer of the reactants. It is worth mention that, there is almost no Pd NPs aggregation or losing during the reaction process, and the prepared catalysts still showed good catalytic activity and physical stability after recycling. Moreover, the catalyst shows potential for catalytic reduction of nitroarenes in a fixed bed reactor, thus could be used for continuously treat nitroarenes polluted water.

The genetic admixture in Tibetan-Yi Corridor.

OBJECTIVES: The Tibetan-Yi Corridor located on the eastern edge of Tibetan Plateau is suggested to be the key region for the origin and diversification of Tibeto-Burman speaking populations and the main route of the peopling of the Plateau. However, the genetic history of the populations in the Corridor is far from clear due to limited sampling in the northern part of the Corridor. MATERIALS AND METHODS: We collected blood samples from 10 Tibetan and 10 Han Chinese individuals from Gansu province and genotyped about 600,000 genome-wide single nucleotide polymorphisms (SNPs). RESULTS: Our data revealed that the populations in the Corridor are all admixed on a genetic cline of deriving ancestry from Tibetans on the Plateau and surrounding lowland East Asians. The Tibetan and Han Chinese groups in the north of the Plateau show significant evidence of low-level West Eurasian admixture that could be probably traced back to 600∼900 years ago. DISCUSSION: We conclude that there have been huge population migrations from surrounding lowland onto the Tibetan Plateau via the Tibetan-Yi Corridor since the initial formation of Tibetans probably in Neolithic Time, which leads to the current genetic structure of Tibeto-Burman speaking populations.