A trinary support of Ni/NiO/C to immobilize Ir nanoclusters for alkaline hydrogen oxidation.

The hydrogen oxidation reaction is an important process in anion exchange membrane fuel cells with alkaline solutions. The pursuit of efficient catalysts for alkaline hydrogen oxidation has attracted considerable attention. In this study, we present a precursor route for the synthesis of a new Ir-based catalyst (Ir-Ni/NiO/C), in which Ir nanoclusters were immobilized on the generated Ni/NiO/C support derived from a metal-organic framework. The small size of Ir clusters facilitates the exposure of catalytically active sites. The electronic interplay between the Ir nanoclusters and the Ni/NiO/C support optimized the hydrogen binding energy (HBE) and hydroxide binding energy (OHBE) on the surface, which is unattainable on the contrasting Ir-C, Ir-Ni/C, and Ir-NiO/C products. The optimized catalyst shows excellent mass activity for alkaline hydrogen oxidation, which is 3.1 times that of the Pt/C catalyst. This study presents a promising pathway for the development of advanced HOR catalysts.

Microstructural tailoring of porous few-layer graphene-like biochar from kitchen waste hydrolysis residue in molten carbonate medium: Structural evolution and conductive additive-free supercapacitor application.

Biomass-derived graphene-like material is a promising candidate for supercapacitor electrodes, while it is critical to controllably convert biomass into structure-tunable graphene. Herein, few-layer graphene-like biochar (FLGBS) was successfully fabricated from waste biomass in molten carbonate medium. Molten carbonate acted as the effective catalyst for graphitizing and the liquid medium for microcrystal relinking to achieve the rearrangement of carbon structure. It was found that the stacking of graphene layer and formation of porous structure were influenced by the volume of reaction medium and biomass pre­carbonation. Namely, increasing the dosage of molten K2CO3 was in favor to form few layer-type graphene structure, but excess dosage could destroy the nanopore structure to expand the aperture. In addition, pre­carbonation at high temperature impeded the exfoliation of graphene layers. When FLGBSs were applied to fabricate conductive additive-free electrode, they displayed a superior supercapacitor performance (up to 237.4 F g-1 at 0.5 Ag-1). This excellent performance should be attributed to the large specific surface area, hierarchical pore structure and graphene-like structure. In short, this work could help to get insights into the structural evolution of biomass carbon to graphene-like biochar in molten carbonate medium and achieve the tailoring of microstructure for further application in energy storage.

Degradation and phosphorus immobilization treatment of organophosphate esters hazardous waste by Fe-Mn bimetallic oxide.

Organophosphate esters (OPEs) waste is difficult to dispose effectively because of its stability and the potential risk of P element. In this study, taking one typical organic extractant of tributyl phosphate (TBP) as an example, we proposed a strategy to treat OPEs inspired by chemical looping combustion (CLC) technology-oxygen carrier immobilization process (OCIP), aiming at efficient TBP degradation and simultaneous P immobilization. Adopting Fe-Mn bimetallic oxide (FMBO) as oxygen carrier, an almost 100% P immobilization efficiency was achieved under recommended conditions which were obtained by response surface methodology. Meanwhile, gaseous products released from TBP degradation, e.g., non-methane hydrocarbon, was lower than the maximum allowable emission concentration limit. Further characterizations implied that P-species released from reaction process were mainly immobilized as stable inorganic forms of metaphosphate, phosphate and pyrophosphate. On the basis of identifying degradation intermediates, we proposed a possible degradation pathways. FMBO as an oxygen carrier provided sufficient oxygen molecules for flameless combustion of OCIP process. Electron paramagnetic resonance measurement confirmed the existence of oxygen vacancies on FMBO surface, which contributed to the formation of •O2-. Oxidation by oxygen molecules and •O2- attack resulted in the degradation and mineralization of TBP, with simultaneously achieving P stabilization.

Tributyl phosphate degradation and phosphorus immobilization by MnO2: Reaction condition optimization and mechanism exploration.

The treatment of tributyl phosphate (TBP) extractant waste from specific industry, eg., nuclear industry, is a great challenge due to its stability and high environmental risk of phosphorus-containing species releasing. Inspired by chemical looping combustion (CLC) technology, a MnO2-assisted thermal oxidation strategy is proposed for TBP degradation and simultaneously P immobilization. Under recommended reaction conditions of 220 °C, 10 g MnO2 mL-1 TBP and 3 h reaction duration, a high P immobilization efficiency of 93.99% is achieved. Material characterization results indicate that P is mainly immobilized in the form of Mn2P2O7, which greatly reduces the environmental risk of P-containing species. TBP degradation intermediates are further identified by thermogravimetric-gas chromatography-mass spectrometry (TG-GC-MS), liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS), which facilitates understanding of reaction mechanisms as well as proposing possible pathways of TBP degradation. It is suggested that MnO2 provides essential oxygen as oxygen carrier for flameless combustion. Meantime, MnO2 reduction leads to the generation of Mn(III) species. The existence of oxygen vacancy in MnO2 also facilitates •O2- radical generation. Under flameless combustion and attacks of Mn(III) and •O2-, TBP is firstly degraded into intermediates and finally mineralized into CO2 and H2O, while P is mainly immobilized as pyrophosphate.

Effect of Nb2O5 doping on improving the thermo-mechanical stability of sealing interfaces for solid oxide fuel cells.

Nb2O5 is added to a borosilicate sealing system to improve the thermo-mechanical stability of the sealing interface between the glass and Fe-Cr metallic interconnect (Crofer 22APU) in solid oxide fuel cells (SOFCs). The thermo-mechanical stability of the glass/metal interface is evaluated experimentally as well as by using a finite element analysis (FEA) method. The sealing glass doped with 4 mol.% Nb2O5 shows the best thermo-mechanical stability, and the sealing couple of Crofer 22APU/glass/GDC (Gd0.2Ce0.8O1.9) remains intact after 50 thermal cycles. In addition, all sealing couples show good joining after being held at 750 °C for 1000 h. Moreover, the possible mechanism on the thermo-mechanical stability of sealing interface is investigated in terms of stress-based and energy-based perspectives.