Melamine-assisted synthesis of paper mill sludge-based carbon nanotube/nanoporous carbon nanocomposite for enhanced electrocatalytic oxygen reduction activity

Developing efficient and cheap electrocatalysts as substitutes for commercial Pt/C in the oxygen reduction reaction(ORR)is extremely necessary. Herein, paper mill sludge (PMS) was utilized to produce iron, nitrogen and sulfur co-doped carbon nanotube/nanoporous carbon nanocomposite (PMS-CNT/C) by pyrolysis. PMS-CNT/C-b, one of as-prepared PMS-CNT/C exhibited excellent oxygen reduction reaction activity with an onset potential of 0.99 V vs. RHE and half-wave potential of 0.77 V vs. RHE, which was similar to the commercial Pt/C catalyst (onset potential of 0.99 V vs. RHE and half-wave potential of 0.76 V vs. RHE). It had longer-term stability and higher methanol tolerance in alkaline medium than Pt/C. Moreover, the new catalyst also exhibited excellent catalytic performance in neutral solution. The energy output of microbial fuel cells loaded with PMS-CNT/C-b catalyst was also higher than that of commercial Pt/C under neutral condition. The excellent ORR performance of PMS-CNT/C-b was due to the carbon nanotube/nanoporous structure and the synergistic effect of abundant N groups, iron nitrides and thiophene-S. The formation of CNTs in the carbon nanotube/nanoporous carbon nanocomposite was mainly attributed to melamine, which was added into PMS and was at first just considered as a nitrogen source to develop N-doped PMS-based catalysis in this work. The synthesis of paper mill sludge-based carbon nanotube/nanoporous nanocomposite and its excellent ORR activity will make the new catalyst a promising cathodic electrocatalyst alternative for fuel cells.     

Solidification of glass-ceramics of simulated fission products RE3+, Sr2+, Ba2+ in chlorine-containing waste molten salt

Embedding nuclear waste in glass-ceramic and immobilizing nuclides in ceramic lattice is an effective way for the disposal of high-level radioactive waste. In this paper, a method of solidification of simulated various nuclides was proposed, i.e., RE³⁺(RE = La, Sm, Nd, Dy), Sr²⁺ and Ba²⁺ precipitated from waste molten salt in the form of REPO₄, SrCO₃ and BaCO₃ were solidified in glass-ceramics. To avoid the decomposition of SrCO₃ and BaCO₃ at high temperature, SrCO₃/BaCO₃ containing Cl⁻ salt was further sintered with NH₄H₂PO₄ to form Sr₅(PO₄)₃Cl/Ba₅(PO₄)₃Cl ceramics. It was found that the prepared REPO₄ belonged to monoclinic or tetragonal crystal system, while Sr₅(PO₄)₃Cl and Ba₅(PO₄)₃Cl belonged to hexagonal crystal system. REPO₄, Sr₅(PO₄)₃Cl and Ba₅(PO₄)₃Cl ceramics were co-solidified in iron phosphate glass. BET results showed that the ceramics had a dense structure without any pore inside. XRD, TEM and HRTEM results showed all ceramics had high crystallinity, and nuclides could enter the lattice structure of ceramics through isomorphic replacement, which made the nuclides stable in the crystal structure. The effects of embedding rate on the volume density, Vickers hardness and wettability of glass-ceramics were explored. It was found that the density of the glass-ceramics gradually increased with the increase of ceramic embedding rate, however, the Vickers hardness firstly increased and then decreased. When the embedding rate reached 20 wt%, the Vickers hardness of the glass-ceramics could reach 583.90 GPa. The water contact angles of glass-ceramics with an embedding rate 0–40 wt% were measured to be 70.45°–84.05°, indicating glass-ceramics having a good water leaching resistance. Furthermore, the normalized leaching rate NR_i of La³⁺, Sm³⁺, Nd³⁺, Dy³⁺, Sr²⁺, Ba²⁺, Cl⁻ on the 28th day were estimated to be 7.53 × 10⁻⁷, 5.02 × 10⁻⁷, 5.12 × 10⁻⁷, 4.04 × 10⁻⁷, 1.22 × 10⁻³, 1.59 × 10⁻⁴, 1.07 × 10⁻⁴ g‧m⁻²‧d⁻¹, which indicating that all elements remained good leaching resistance.     

Fabrication and thermal shock behavior of periclase-forsterite aggregates with micro-nanometer dual-pore-size structures

To improve the service life of periclase-forsterite refractories, it is important to develop aggregates with high thermal shock resistance. In this study, periclase-forsterite aggregates with good resistance to thermal shock and micro-nanopores were prepared using high-silicon magnesite, silica, and silica sol. Microcracks were generated in the multiphase aggregates, which inhibited the continuous propagation of cracks during thermal shock through mismatched thermal expansion coefficients. Based on Hasselman's thermal shock stability factor, the reduction in the average thermal expansion coefficient and improved mechanical characteristics were critical factors in improving the thermal shock resistance of the multiphase aggregates. As a binder, silica sol provided nano-SiO₂ and superplasticity, which facilitated the formation of micro-nanopores and strengthened the combination of the various phases in the aggregates.