Metal borides have attracted the attention of researchers due to their useful physical properties and unique ability to form high hydrogen-capacity metal borohydrides. We demonstrate improved hydrogen storage properties of a nanoscale Mg–B material made by surfactant ball milling MgB2 in a mixture of heptane, oleic acid, and oleylamine. Transmission electron microscopy data show that Mg–B nanoplatelets are produced with sizes ranging from 5 to 50 nm, which agglomerate upon ethanol washing to produce an agglomerated nanoscale Mg–B material of micron-sized particles with some surfactant still remaining. X-ray diffraction measurements reveal a two-component material where 32% of the solid is a strained crystalline solid maintaining the hexagonal structure with the remainder being amorphous. Fourier transform infrared shows that the oleate binds in a “bridge-bonding” fashion preferentially to magnesium rather than boron, which is confirmed by density functional theory calculations. The Mg–B nanoscale material is deficient in boron relative to bulk MgB2 with a Mg–B ratio of ∼1:0.75. The nanoscale MgB0.75 material has a disrupted B–B ring network as indicated by X-ray absorption measurements. Hydrogenation experiments at 700 bar and 280 °C show that it partially hydrogenates at temperatures 100 °C below the threshold for bulk MgB2 hydrogenation. In addition, upon heating to 200 °C, the H–H bond-breaking ability increases ∼10-fold according to hydrogen–deuterium exchange experiments due to desorption of oleate at the surface. This behavior would make the nanoscale Mg–B material useful as an additive where rapid H–H bond breaking is needed.

The integrated application of green chemistry, life cycle thinking, and systems thinking has the potential to reduce environmental impacts related to the use and production of chemical products or materials. Life cycle and systems thinking are key perspectives needed to avoid the unintended consequences or unsubstantiated claims that inhibit development and adoption of more sustainable products. However, systems thinking is rarely taught in the chemistry curriculum. Students need experience evaluating the effects of products on societal and earth systems (i.e., using systems thinking) in order to anticipate trade-offs and make informed design decisions. To give students an immersive learning experience, we developed a sustainable product design project that brings together tools from green chemistry, life cycle thinking, and systems thinking. We found that this experiential learning approach gave students generalizable strategies for innovating and implementing sustainable practices in their current industrial positions. The project was divided into three workshops: in Workshop I they evaluated the life cycle impacts and toxicity for a material of concern, in Workshop II they measured the performance of this material and compared it to alternatives, and in Workshop III they designed a mock-product that was both high performing and environmentally friendly. We piloted this framework with master’s students evaluating polymer foams for use in an infant car seat; however, we envision this project being suitable for a range of other types of products. Moreover, we have suggested ways to adapt the duration and sophistication of the workshops to make them appropriate for a variety of course levels.

Amine-based adsorbents are promising for direct air capture of CO 2 , yet oxidative degradation remains a key unmitigated risk hindering wide-scale deployment. Borrowing wisdom from the basic auto-oxidation scheme, insights are gained into the underlying degradation mechanisms of polyamines by quantum chemical, advanced sampling simulations, adsorbent synthesis, and accelerated degradation experiments. The reaction kinetics of polyamines are contrasted with that of typical aliphatic polymers and they elucidate for the first time the critical role of aminoalkyl hydroperoxide decomposition in the oxidative degradation of amino-oligomers. The experimentally observed variation in oxidative stability of polyamines with different backbone structures is explained by the relationship between the local chemical structure and the free energy barrier of aminoalkyl hydroperoxide decomposition, suggesting that its energetics can be used as a descriptor to screen and design new polyamines with improved stability. The developed computational capability sheds light on radical-induced degradation chemistry of other organic functional materials.

Engineering the interfacial distribution of electrolytic ions can aid in modulating the electrocatalyst performance and efficiency. Using a hybrid quantum-classical modeling approach, we describe how predictive tuning of the solution microenvironment on copper can enhance the efficiency of CO2 reduction (CO2R) to C2 products. We elucidate how competing electrolyte constituents in mixed electrolyte solutions stimulate restructuring of the electrochemical double layer (EDL) and stabilize the OCCO* dimer (* denotes surface adsorbed), with predictions validated in flow reactors using copper gas diffusion electrodes (Cu-GDEs). Our findings highlight how molecular-scale electrolyte engineering with informed models of the EDL can be leveraged to tailor CO2R activity and selectivity toward C2 products.