Controllably partial removal of thiolate ligands from unsupported Au_(25) nanoclusters by rapid thermal treatments for electrochemical CO_(2)reduction

Colloidal synthesis of metal nanoclusters will inevitably lead to the blockage of catalytically active sites by organic ligands.Here,taking[Au_(25)(PET)_(18)]-(PET=2-phenylethanethiol)nanocluster as a model catalyst,this work reports a feasible procedure to achieve the controllably partial removal of thiolate ligands from unsupported[Au_(25)(PET)_(18)]-nanoclusters with the preservation of the core structure.This procedure shortens the processing duration by rapid heating and cooling on the basis of traditional annealing treatment,avoiding the reconfiguration or agglomeration of Au_(25)nanoclusters,where the degree of dethiolation can be regulated by the control of duration.This work finds that a moderate degree of dethiolation can expose the Au active sites while maintaining the suppression of the competing hydrogen evolution reaction.Consequently,the activity and selectivity towards CO formation in electrochemical CO_(2)reduction reaction of Au_(25)nanoclusters can be promoted.This work provides a new approach for the removal of thiolate ligands from atomically precise gold nanoclusters.

Biosorption and retention of orthophosphate onto Ca(OH)_2-pretreated biomass of Phragmites sp.

The biosorption of phosphorus in the form of orthophosphate（Po） from wastewater using biomass as the sorbent is of potential importance because the Po-loaded biomass could be applied in the agricultural sector as fertilizer and soil conditioner. However, biomass generally displays a very low affinity for Posorption and therefore biomass surface modification is required. In the present study, the biomass（as model grinded leaves of Phragmites sp. were used）was pretreated with Ca（OH）2to enhance Pobiosorption capacity（qe）. The results indicate that the alkaline pretreatment resulted in a modification of surface functional groups. It was concluded that the main sorption mechanisms were ligand exchange and electrostatic attraction. A series of experiments were conducted to investigate the performance of the pretreated biomass for Pouptake under various conditions. Isotherm and thermodynamic studies were also applied and analyzed. The biosorption process was best described by the pseudo-second order kinetic model and Langmuir isotherm, which gave a qmaxof 12.27 mg P/g at 25°C and p H 7. The Ca（OH）2treated Phragmites biomass applied in this study for Porecovery may present some potential advantages in terms of costs and environmental impact.