Energetics of van der Waals Adsorption on the Metal-Organic Framework NU-1000 with Zr6-oxo, Hydroxo, and Aqua Nodes.

We report measurements of adsorption isotherms and the determination of the isosteric heats of adsorption of several small gases (H2, D2, Ne, N2, CO, CH4, C2H6, Ar, Kr, and Xe) on the metal-organic framework (MOF) NU-1000, which is one of the most thermally stable MOFs. It has transition-metal nodes of formula Zr6(µ3-OH)4(µ3-O)4(OH)4(OH2)4 that resemble hydrated ZrO2 clusters and can serve as catalysts or catalyst supports. The linkers in this MOF are pyrenes linked to the nodes via the carboxylate groups of benzoates. The broad range of adsorbates studied here allows us to compare trends both with adsorption on other surfaces and with density functional calculations also presented here. The experimental isotherms indicate similar filling of the MOF surface by the different gases, starting with strong adsorption sites near the Zr atoms, a result corroborated by the density functional calculations. This adsorption is followed by the filling of other adsorption sites on the nodes and organic framework. Capillary condensation occurs in wide pores after completion of a monolayer. The total amount adsorbed for all the gases is the equivalent of two complete monolayers. The experimental isosteric heats of adsorption are nearly proportional to the atom-atom (or molecule-molecule) Lennard-Jones well-depth parameters of the adsorbates but ∼13-fold larger. The density functional calculations show a similar trend but with much more scatter and heats that are usually greater (by 30%, on average).

Greenhouse gas emissions for refrigerant choices in room air conditioner units.

In this work, potential replacement refrigerants for window-mounted room air conditioners (RACs) in the U.S. have been evaluated using a greenhouse gas (GHG) emissions analysis. CO(2)-equivalent emissions for several hydrofluoroethers (HFEs) and other potential replacements were compared to the most widely used refrigerants today. Included in this comparison are pure refrigerants that make up a number of hydrofluorocarbon (HFC) mixtures, pure hydrocarbons, and historically used refrigerants such as propane and ammonia. GHG emissions from direct and indirect sources were considered in this thermodynamic analysis. Propylene, dimethyl ether, ammonia, R-152a, propane, and HFE-152a all performed effectively in a 1 ton window unit and produced slightly lower emissions than the currently used R-22 and R-134a. The results suggest that regulation of HFCs in this application would have some effect on reducing emissions since end-of-life emissions remain at 55% of total refrigerant charge despite EPA regulations that mandate 80% recovery. Even so, offsite emissions due to energy generation dominate over direct GHG emissions and all the refrigerants perform similarly in totals of indirect GHG emissions.

Carbon dioxide emission implications if hydrofluorocarbons are regulated: a refrigeration case study.

The U.S. is strongly considering regulating hydrofluorocarbons (HFCs) due to their global climate change forcing effects. A drop-in replacement hydrofluoroether has been evaluated using a gate-to-grave life cycle assessment of greenhouse gas emissions for the trade-offs between direct and indirect carbon dioxide equivalent emissions compared to a current HFC and a historically used refrigerant. The results indicate current regulations being considered may increase global climate change.