Supra-Photothermal CO2 Methanation over Greenhouse-Like Plasmonic Superstructures of Ultrasmall Cobalt Nanoparticles.

Improving the solar-to-thermal energy conversion efficiency of photothermal nanomaterials at no expense of other physicochemical properties, e.g., the catalytic reactivity of metal nanoparticles, is highly desired for diverse applications but remains a big challenge. Herein, a synergistic strategy is developed for enhanced photothermal conversion by a greenhouse-like plasmonic superstructure of 4 nm cobalt nanoparticles while maintaining their intrinsic catalytic reactivity. The silica shell plays a key role in retaining the plasmonic superstructures for efficient use of the full solar spectrum, and reducing the heat loss of cobalt nanoparticles via the nano-greenhouse effect. The optimized plasmonic superstructure catalyst exhibits supra-photothermal CO2 methanation performance with a record-high rate of 2.3 mol gCo -1 h-1 , close to 100% CH4 selectivity, and desirable catalytic stability. This work reveals the great potential of nanoscale greenhouse effect in enhancing photothermal conversions through the combination with conventional promoting strategies, shedding light on the design of efficient photothermal nanomaterials for demanding applications.

Modulation of the Structure-function Relationship of the "nano-greenhouse effect" towards Optimized Supra-photothermal Catalysis.

Photothermal catalytic CO2 hydrogenation holds great promise for relieving the global environment and energy crises. The "nano-greenhouse effect" has been recognized as a crucial strategy for improving the heat management capabilities of a photothermal catalyst by ameliorating the convective and radiative heat losses. Yet it remains unclear to what degree the respective heat transfer and mass transport efficiencies depend on the specific structures. Herein, the structure-function relationship of the "nano-greenhouse effect" was investigated and optimized in a prototypical Ni@SiO2 core-shell catalyst towards photothermal CO2 catalysis. Experimental and theoretical results indicate that modulation of the thickness and porosity of the SiO2 nanoshell leads to variations in both heat preservation and mass transport properties. This work deepens the understandings on the contributing factor of the "nano-greenhouse effect" towards enhanced photothermal conversion. It also provides insights on the design principles of an ideal photothermal catalyst in balancing heat management and mass transport processes.

Mo2TiC2 MXene-Supported Ru Clusters for Efficient Photothermal Reverse Water-Gas Shift.

Driving metal-cluster-catalyzed high-temperature chemical reactions by sunlight holds promise for the development of negative-carbon-footprint industrial catalysis, which has yet often been hindered by the poor ability of metal clusters to harvest and utilize the full spectrum of solar energy. Here, we report the preparation of Mo2TiC2 MXene-supported Ru clusters (Ru/Mo2TiC2) with pronounced broadband sunlight absorption ability and high sintering resistance. Under illumination of focused sunlight, Ru/Mo2TiC2 can catalyze the reverse water-gas shift (RWGS) reaction to produce carbon monoxide from the greenhouse gas carbon dioxide and renewable hydrogen with enhanced activity, selectivity, and stability compared to their nanoparticle counterparts. Notably, the CO production rate of MXene-supported Ru clusters reached 4.0 mol·gRu-1·h-1, which is among the best reported so far for photothermal RWGS catalysts. Detailed studies suggest that the production of methane is kinetically inhibited by the rapid desorption of CO from the surface of the Ru clusters.

Tailoring the Salt Transport Flux of Solar Evaporators for a Highly Effective Salt-Resistant Desalination with High Productivity.

Developing highly effective salt-resistant solar evaporators for a long-term desalination with a high evaporation rate and water production rate remains a great challenge. Herein, we fabricated a three-dimensional printed hierarchical porous reduced graphene oxide/carbon black (3DP-HP rGO/CB) solar evaporator constructed with a thin layer of porous photothermal interface and a grid of hierarchical porous transport channel possessing a large-sized porous microstructure. The 3DP-HP rGO/CB solar evaporator demonstrates a tailored high-salt transport flux of up to 4.3 kg·m-2·h-1, which displays a highly effective salt-resistant performance at a high evaporation rate of 10.5 kg·m-2·h-1 during a desalination of 10 wt % NaCl brine under 8 kW·m-2 illumination. Experiments and theoretical calculations prove that the large porous microstructure with abundant and low-resistance salt ion channels endows solar evaporators with a high salt transport flux, therefore boosting salt resistance compared to traditional solar evaporators. A 10 d desalination experiment shows the long-term salt resistance of a 3DP-HP rGO/CB solar evaporator for a high-rate and stable evaporation and water production. Furthermore, the 3DP-HP rGO/CB evaporator can purify 10 wt % NaCl brine at an ultrafast water production rate of up to 5.6 L·m-2·h-1 under natural sunlight. This work demonstrates great potential for the practical implementation of solar desalination with high productivity.

Niobium and Titanium Carbides (MXenes) as Superior Photothermal Supports for CO2 Photocatalysis.

The conversion of CO2 into fuels and feedstock chemicals via photothermal catalysis holds promise for efficient solar energy utilization to tackle the global energy shortage and climate change. Despite recent advances, it is of emerging interest to explore promising materials with excellent photothermal properties to boost the performance of photothermal CO2 catalysis. Here, we report the discovery of MXene materials as superior photothermal supports for metal nanoparticles. As a proof-of-concept study, we demonstrate that Nb2C and Ti3C2, two typical MXene materials, can enhance the photothermal effect and thus boost the photothermal catalytic activity of Ni nanoparticles. A record CO2 conversion rate of 8.50 mol·gNi-1·h-1 is achieved for Nb2C-nanosheet-supported Ni nanoparticles under intense illumination. Our study bridges the gap between photothermal MXene materials and photothermal CO2 catalysis toward more efficient solar-to-chemical energy conversions and stimulates the interest in MXene-supported metal nanoparticles for other heterogeneous catalytic reactions, particularly driven by sunlight.

Cobalt Plasmonic Superstructures Enable Almost 100% Broadband Photon Efficient CO2 Photocatalysis.

The efficiency of heterogeneous photocatalysis for converting solar to chemical energy is low on a per photon basis mainly because of the difficulty of capturing and utilizing light across the entire solar spectral wavelength range. This challenge is addressed herein with a plasmonic superstructure, fashioned as an array of nanoscale needles comprising cobalt nanocrystals assembled within a sheath of porous silica grown on a fluorine tin oxide substrate. This plasmonic superstructure can strongly absorb sunlight through different mechanisms including enhanced plasmonic excitation by the hybridization of Co nanoparticles in close proximity, as well as inter- and intra-band transitions. With nearly 100% sunlight harvesting ability, it drives the photothermal hydrogenation of carbon dioxide with a 20-fold rate increase from the silica-supported cobalt catalyst. The present work bridges the gap between strong light-absorbing plasmonic superstructures with photothermal CO2 catalysis toward the complete utilization of the solar energy.