Xianyin Chen

Metal–organic framework with optimally selective xenon adsorption and separation

Nuclear energy is among the most viable alternatives to our current fossil fuel-based energy economy. The mass deployment of nuclear energy as a low-emissions source requires the reprocessing of used nuclear fuel to recover fissile materials and mitigate radioactive waste. A major concern with reprocessing used nuclear fuel is the release of volatile radionuclides such as xenon and krypton that evolve into reprocessing facility off-gas in parts per million concentrations. The existing technology to remove these radioactive noble gases is a costly cryogenic distillation; alternatively, porous materials such as metal–organic frameworks have demonstrated the ability to selectively adsorb xenon and krypton at ambient conditions. Here we carry out a high-throughput computational screening of large databases of metal–organic frameworks and identify SBMOF-1 as the most selective for xenon. We affirm this prediction and report that SBMOF-1 exhibits by far the highest reported xenon adsorption capacity and a remarkable Xe/Kr selectivity under conditions pertinent to nuclear fuel reprocessing.

Direct Observation of Xe and Kr Adsorption in a Xe-Selective Microporous Metal-Organic Framework

The cryogenic separation of noble gases is energy-intensive and expensive, especially when low concentrations are involved. Metal-organic frameworks (MOFs) containing polarizing groups within their pore spaces are predicted to be efficient Xe/Kr solid-state adsorbents, but no experimental insights into the nature of the Xe-network interaction are available to date. Here we report a new microporous MOF (designated SBMOF-2) that is selective toward Xe over Kr under ambient conditions, with a Xe/Kr selectivity of about 10 and a Xe capacity of 27.07 wt % at 298 K. Single-crystal diffraction results show that the Xe selectivity may be attributed to the specific geometry of the pores, forming cages built with phenyl rings and enriched with polar -OH groups, both of which serve as strong adsorption sites for polarizable Xe gas. The Xe/Kr separation in SBMOF-2 was investigated with experimental and computational breakthrough methods. These experiments showed that Kr broke through the column first, followed by Xe, which confirmed that SBMOF-2 has a real practical potential for separating Xe from Kr. Calculations showed that the capacity and adsorption selectivity of SBMOF-2 are comparable to those of the best-performing unmodified MOFs such as NiMOF-74 or Co formate.

Magnetic Hydrogels from Alkyne/Cobalt Carbonyl-Functionalized ABA Triblock Copolymers

A series of alkyne-functionalized poly(4-(phenylethynyl)styrene)-block-poly(ethylene oxide)-block-poly(4-(phenylethynyl)styrene) (PPES-b-PEO-b-PPES) ABA triblock copolymers was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. PESn[Co2(CO)6]x-EO800-PESn[Co2(CO)6]x ABA triblock copolymer/cobalt adducts (10-67 wt % PEO) were subsequently prepared by reaction of the alkyne-functionalized PPES block with Co2(CO)8 and their phase behavior was studied by TEM. Heating triblock copolymer/cobalt carbonyl adducts at 120 °C led to cross-linking of the PPES/Co domains and the formation of magnetic cobalt nanoparticles within the PPES/Co domains. Magnetic hydrogels could be prepared by swelling the PEO domains of the cross-linked materials with water. Swelling tests, rheological studies and actuation tests demonstrated that the water capacity and modulus of the hydrogels were dependent upon the composition of the block copolymer precursors.

Photocatalytic hydrogen evolution using nanocrystalline gallium oxynitride spinel

Photocatalytic hydrogen evolution from water was observed over nanocrystalline gallium oxynitride spinel under simulated solar light irradiation (320 nm < λ < 800 nm). Up to 8 μmol h−1 of H2 was evolved without co-catalyst loading. The photocatalyst was synthesized by the ammonolysis of gallium nitrate hydrate (Ga(NO3)3·xH2O). Optical measurements indicate an indirect gap (Eg) in the visible region (Eg = 2.50 eV) which is ascribed to photoexcitations from the N 2p valence states. A direct gap has an onset at ultraviolet energies (Eg = 3.69 eV), which is ascribed to photoexcitations from lower energy O 2p valence states.

Iodine Adsorption in Metal Organic Frameworks in the Presence of Humidity

Used nuclear fuel reprocessing represents a unique challenge when dealing with radionuclides such as isotopes of 85Kr and 129I2 due to their volatility and long half-life. Efficient capture of 129I2 ( t1/2 = 15.7 × 106 years) from the nuclear waste stream can help reduce the risk of releasing I2 radionuclide into the environment and/or potential incorporation into the human thyroid. Metal organic frameworks have the reported potential to be I2 adsorbents but the effect of water vapor, generally present in the reprocessing off-gas stream, is rarely taken into account. Moisture-stable porous metal organic frameworks that can selectively adsorb I2 in the presence of water vapor are thus of great interest. Herein, we report on the I2 adsorption capacity of two microporous metal organic frameworks at both dry and humid conditions. Single-crystal X-ray diffraction and Raman spectroscopy reveal distinct sorption sites of molecular I2 within the pores in proximity to the phenyl- and phenol-based linkers stabilized by the I···π and I···O interactions, which allow selective uptake of iodine.

Effects of copper loading on NH3-SCR and NO oxidation over Cu impregnated CHA zeolite

Cu/CHA catalysts with various Cu loadings (0.5 wt%–6.0 wt%) were synthesized via incipient wetness impregnation. The catalysts were applied to the selective catalytic reduction (SCR) of NO with NH3 and NO oxidation reaction. XRD and N2 adsorption-desorption data showed that CHA structure was maintained with the incorporation of Cu, while specific surface areas decreased with increasing Cu loading. At intermediate Cu loading, 4 wt%, the highest NH3-SCR activity was observed with ∼98% N2 selectivity from 150 °C to 300 °C. Small amounts of water, 2%, slightly increased NO conversion in addition to the remarkable N2O and NO2 reduction at high temperature. Water effects are attributed to the improved Cu ion reducibility and mobility. NO oxidation results provided no relation between NO2 formation and SCR activity. Physicochemical properties, NO conversion, N2 selectivity, and activation energy data showed that impregnated samples’ molecular structure and catalytic activity are comparable to the conventional ion-exchanged (IE) samples’ ones.