High-Performance Planar Thin Film Thermochromic Window via Dynamic Optical Impedance Matching

Window coatings with dynamic solar transmittance represent an excellent opportunity to reduce building heating and cooling loads, which account for >40% of energy consumed by the built environment. In particular, inorganic vanadium dioxide-based thermochromic coatings offer long lifetimes (>30 years) and can be passively integrated into a window system without additional electronics or power requirements. However, their limited solar modulation depth and wide phase-change hysteresis have traditionally restricted their ability to adapt to changing weather conditions. Here, we derive an optical performance limit for thin film vanadium dioxide coatings, which we find to be far beyond the current literature. Furthermore, we experimentally demonstrate a solution-processed multilayer thin film coating that uses temperature-dependent optical impedance matching to approach the optical performance limit. The thin film coating demonstrated has a record solar transmittance modulation of 21.8% while maintaining a high level of visible transparency (∼50%) and minimal hysteresis (∼10 °C). This work represents a step-change in thin film thermochromic window coatings and, as a result, establishes planar thin film vanadium dioxide as the most viable morphology for high-performance thermochromic windows

Directed evolution of artificial repeat proteins as habit modifiers for the morphosynthesis of (111)-terminated gold nanocrystals

Natural biocomposites are shaped by proteins that have evolved to interact with inorganic materials. Protein directed evolution methods which mimic Darwinian evolution have proven highly successful to generate improved enzymes or therapeutic antibodies but have rarely been used to evolve protein–material interactions. Indeed, most reported studies have focused on short peptides and a wide range of oligopeptides with chemical binding affinity for inorganic materials have been uncovered by phage display methods. However, their small size and flexible unfolded structure prevent them from dictating the shape and crystallinity of the growing material. In the present work, a specific set of artificial repeat proteins (αRep), which exhibit highly stable 3D folding with a well-defined hypervariable interacting surface, is selected by directed evolution of a very efficient home-built protein library for their high and selective affinity for the Au(111) surface. The proteins are built from the extendable concatenation of self-compatible repeated motifs idealized from natural HEAT proteins. The high-yield synthesis of Au(111)-faceted nanostructures mediated by these αRep proteins demonstrates their chemical affinity and structural selectivity that endow them with high crystal habit modification performances. Importantly, we further exploit the protein shell spontaneously assembled on the nanocrystal facets to drive protein-mediated colloidal self-assembly and on-surface enzymatic catalysis. Our method constitutes a generic tool for producing nanocrystals with determined faceting, superior biocompatibility and versatile bio-functionalization towards plasmon-based devices and (bio)molecular sensors

The impact of bead milling on the thermodynamics and kinetics of the structural phase transition of VO2 particulate materials and their potential for use in thermochromic glazing

The thermodynamics and kinetics of the structural phase transition from monoclinic VO2 (M) to rutile VO2 (R) and vice versa were studied for particulate materials obtained by bead milling of VO2 (M) powder. Using wet bead milling, we decreased the particle size of VO2 (M) powder from ∼1 μm to 129 nm. With progressive milling, the switching enthalpy decreased from 47 J g−1 to 29 J g−1 due to a loss of crystallinity. The switching kinetics were studied using Friedman's differential isoconversional method. The activation energy |Eα| decreases with increasing difference between the actual temperature of the material and its switching temperature (T0). Furthermore, |Eα| decreases with progressive milling, and kinetic asymmetry is induced. For milled particulate materials, |Eα| is lower for the switch from VO2 (R) to VO2 (M) than for the opposite switch. For hydrothermally synthesized nanoparticles, |Eα| is in the same order of magnitude, albeit with inverse switching asymmetry. Latter may result from different defects that are introduced during both preparation techniques. Applying layers of milled particulate material to glass sheets yielded thermochromic coatings with luminous transmission of 40.7% and solar modulation of 8.3%. This demonstrates that milled VO2 particles have potential for use in energy efficient thermochromic windows

Combined Effect of Temperature Induced Strain and Oxygen Vacancy on Metal-Insulator Transition of VO2 Colloidal Particles

Vanadium dioxide (VO2) is a promising material in the development of thermal and electrically sensitive devices due to its first order reversible metal-insulator transition (MIT) at 68 °C. Such high MIT temperature (TC) largely restricts its widespread application which could be enabled if a straightforward tuning mechanism were present. Here this need is addressed through a facile approach that uses the combined effects of temperature induced strain and oxygen vacancies in bulk VO2 colloidal particles. A simple thermal annealing process under varying vacuum is used to achieve phase transformation of metastable VO2(A) into VO2(M2), (M2+M3), (M1) and higher valence V6O13 phases. During this process, distinct multiple phase transitions including increased as well as suppressed TC are observed with respect to the annealing temperature and varied amount of oxygen vacancies respectively. The latent heat of phase transition is also significantly improved upon thermal annealing by increasing the crystallinity of the samples. This work not only offers a facile route for selective phase transformation of VO2 as well as to manipulate the phase transition temperature, but also contributes significantly to the understanding of the role played by oxygen vacancies and temperature induced stress on MIT which is essential for VO2 based applications