Molecular basis of activity changes in acid catalysis within nanoconfined water
Related Articles
Stiff and self-healing hydrogels by polymer entanglements in co-planar nanoconfinement
Many biological tissues are mechanically strong and stiff but can still heal from damage. By contrast, synthetic hydrogels have not shown comparable combinations of properties, as current stiffening approaches inevitably suppress the required chain/bond dynamics for self-healing. Here we show a stiff and self-healing hydrogel with a modulus of 50 MPa and tensile strength up to 4.2 MPa by polymer entanglements in co-planar nanoconfinement. This is realized by polymerizing a highly concentrated monomer solution within a scaffold of fully delaminated synthetic hectorite nanosheets, shear oriented into a macroscopic monodomain. The resultant physical gels show self-healing efficiency up to 100% despite the high modulus, and high adhesion shear strength on a broad range of substrates. This nanoconfinement approach allows the incorporation of novel functionalities by embedding colloidal materials such as MXenes and can be generalized to other polymers and solvents to fabricate stiff and self-healing gels for soft robotics, additive manufacturing and biomedical applications.
Solar-driven interfacial evaporation technologies for food, energy and water
Solar-driven interfacial evaporation technologies use solar energy to heat materials that drive water evaporation. These technologies are versatile and do not require electricity, which enables their potential application across the food, energy and water nexus. In this Review, we assess the potential of solar-driven interfacial evaporation technologies in food, energy and clean-water production, in wastewater treatment, and in resource recovery. Interfacial evaporation technologies can produce up to 5.3 l m–2 h−1 of drinking water using sunlight as the energy source. Systems designed for food production in coastal regions desalinate water to irrigate crops or wash contaminated soils. Technologies are being developed to simultaneously produce both clean energy and water through interfacial evaporation and have reached up to 204 W m–2 for electricity and 2.5 l m–2 h–1 for water in separate systems. Other solar evaporation approaches or combinations of approaches could potentially use the full solar spectrum to generate multiple products (such as water, food, electricity, heating or cooling, and/or fuels). In the future, solar evaporation technologies could aid in food, energy and water provision in low-resource or rural settings that lack reliable access to these essentials, but the systems must first undergo rigorous, scaled-up field testing to understand their performance, stability and competitiveness.
Impact of transboundary water flows on quality-induced water pressure in China
Quality-induced water pressure (P) is gaining increased attention. With the flows of transboundary water, P can be transferred among upstream and downstream regions. Here, we quantified the magnitude of pollutant transmission, and assessed its impact on individual provinces in China. On the annual basis, P was mitigated in 61% of provinces for Chemical Oxygen Demand, 87% for Ammonia Nitrogen, and 84% for Total Phosphorus, while it was intensified for 77% for Total Nitrogen in 2021. The aggregated P were mitigated in 68% of provinces, while intensified in 32% provinces. Furthermore, the monthly assessment has found that the impact of transboundary water on P varies seasonally, generally alleviating in winter and exacerbating in summer. This fluctuation was attributed to the comparatively higher quality of transboundary inflows during winter relative to local water quality. This study provides a scientific foundation for effective water management and quality control.
Enantioselective C–H annulations enabled by either nickel- or cobalt-electrocatalysed C–H activation for catalyst-controlled chemodivergence
Enantioselective electrocatalysis shows unique potential for the sustainable assembly of enantiomerically enriched molecules. This approach allows electro-oxidative C–H activation to be performed paired to the hydrogen evolution reaction. Recent progress has featured scarce transition metals with limited availability. Here we reveal that the earth-abundant 3d transition metals nickel and cobalt exhibit distinctive performance for enantioselective electrocatalysis with chemodivergent reactivity patterns. Enantioselective desymmetrizations of strained bicyclic alkenes were achieved through C–H annulations. A data-driven optimization of chiral N,O-bidentate salicyloxazoline-type ligands was crucial for enhancing enantioselectivity in nickel electrocatalysis. Notably, in the transition state of the enantio-determining step, secondary weak attractive π–π and CH–π interactions were identified, reflecting the informed adaptations in the ligand design. Detailed mechanistic investigations by experimental and computational studies revealed for the nickel electrocatalysis a C–N bond-forming reductive elimination from nickel(III) and for the cobalt electrocatalysis a C–C bond-forming nucleophilic addition from cobalt(III) as the product-determining steps.
Geochemistry of lithospheric aqueous fluids modified by nanoconfinement
Water is a principal component of Earth’s fluids, and its interaction with rocks governs lithospheric geochemical and geodynamic processes. Water–rock interactions are crucial in societally relevant resource management, including subsurface extraction and storage of energy, the deep carbon cycle and generating critical metal deposits. The prevailing view is that fluids navigate through the lithosphere without being influenced by the distinct properties that arise from matter confined at the nanoscale. Here we use electron microscopy and neutron scattering data to show that a diverse range of lithospheric rocks, including sandstones, peridotites and serpentinites, consistently show nanoporosity, predominantly with pore sizes < 100 nanometres. Using molecular dynamics simulations, we demonstrate that water’s dielectric permittivity—a fundamental property that governs its geochemical behaviour—diverges in nanoconfinement from its bulk counterpart under conditions ranging from ambient to extremes of 700 °C and 5 GPa. Our geochemical simulations suggest that changes in water permittivity due to confinement will decrease mineral solubility, a process that is not currently considered in models of fluid–rock interactions. Given that permittivity is also intimately linked to ion speciation, pore-size-dependent properties should be expected to exert a primary influence on rock reactivity and the geochemical evolution of fluids during fluid–rock interactions.
Responses