Three-Phase Photocatalysis for the Enhanced Selectivity and Activity of CO2 Reduction on a Hydrophobic Surface.
ABSTRACT: The photocatalytic CO2 reduction reaction (CRR) represents a promising route for the clean utilization of stranded renewable resources, but poor selectivity resulting from the competing hydrogen evolution reaction (HER) in aqueous solution limits its practical applicability. In the present contribution a photocatalyst with hydrophobic surfaces was fabricated. It facilitates an efficient three-phase contact of CO2 (gas), H2 O (liquid), and catalyst (solid). Thus, concentrated CO2 molecules in the gas phase contact the catalyst surface directly, and can overcome the mass-transfer limitations of CO2 , inhibit the HER because of lowering proton contacts, and overall enhance the CRR. Even when loaded with platinum nanoparticles, one of the most efficient HER promotion cocatalysts, the three-phase photocatalyst maintains a selectivity of 87.9?%. Overall, three-phase photocatalysis provides a general and reliable method to enhance the competitiveness of the CRR.
Project description:Photoelectrochemical CO2 reduction into syngas (a mixture of CO and H2) provides a promising route to mitigate greenhouse gas emissions and store intermittent solar energy into value-added chemicals. Design of photoelectrode with high energy conversion efficiency and controllable syngas composition is of central importance but remains challenging. Herein, we report a decoupling strategy using dual cocatalysts to tackle the challenge based on joint computational and experimental investigations. Density functional theory calculations indicate the optimization of syngas generation using a combination of fundamentally distinctive catalytic sites. Experimentally, by integrating spatially separated dual cocatalysts of a CO-generating catalyst and a H2-generating catalyst with GaN nanowires on planar Si photocathode, we report a record high applied bias photon-to-current efficiency of 1.88% and controllable syngas products with tunable CO/H2 ratios (0-10) under one-sun illumination. Moreover, unassisted solar CO2 reduction with a solar-to-syngas efficiency of 0.63% is demonstrated in a tandem photoelectrochemical cell.
Project description:Graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) has been widely studied as a photocatalyst for the splitting of water to produce hydrogen. In order to solve the problems of limited number of active sites and serious recombination rate of charge-carriers, noble metals are needed as cocatalysts. Here, we selectively anchored Pt nanoparticles (NPs) to specific nitrogen species on the surface of g-C<sub>3</sub>N<sub>4</sub> via heat treatment in argon-hydrogen gas mixture, thus achieving g-C<sub>3</sub>N<sub>4</sub> photocatalyst anchored by highly dispersed homogeneous Pt NPs with the co-existed metallic Pt<sup>0</sup> and Pt<sup>2</sup><sup>+</sup> species. The synergistic effect of highly dispersed metallic Pt<sup>0</sup> and Pt<sup>2</sup><sup>+</sup> species makes the catalyst exhibit excellent photocatalytic performance. Under the full-spectrum solar light irradiation, the photocatalytic hydrogen production rate of the photocatalyst is up to 18.67 mmol·g<sup>-1</sup>·h<sup>-1</sup>, which is 5.1 times of the catalyst prepared by non-selective deposition of Pt NPs.
Project description:The K and Sr cations (K+ and Sr2+) in a Sr2KTa5O15 photocatalyst were found to be easily substituted by Na cations (Na+) to form Sr x K y Na z Ta5O15 by a facile one-pot flux method using a mixture of potassium chloride (KCl) and sodium chloride (NaCl). Sr x K y Na z Ta5O15 fabricated using a mixture of KCl and NaCl with a Ag cocatalyst showed enhanced photocatalytic activity without apparent change in selectivity toward CO for the photocatalytic conversion of CO2 using H2O. The present study demonstrates that the flux treatment significantly affected the phase, morphology, band gap, and surface Sr composition of the catalyst owing to the substitution of K+ and Sr2+ for Na+. The stability and durability of the catalyst were also enhanced as compared to those of the photocatalyst fabricated using only KCl flux due to more stable Ag on the surface of Sr x K y Na z Ta5O15.
Project description:Photocatalytic transformation of biomass into value-added chemicals coupled with co-production of hydrogen provides an explicit route to trap sunlight into the chemical bonds. Here, we demonstrate a rational design of Zn<sub>1-x</sub>Cd<sub>x</sub>S solid solution homojunction photocatalyst with a pseudo-periodic cubic zinc blende (ZB) and hexagonal wurtzite (WZ) structure for efficient glucose conversion to simultaneously produce hydrogen and lactic acid. The optimized Zn<sub>0.6</sub>Cd<sub>0.4</sub>S catalyst consists of a twinning superlattice, has a tuned bandgap, and displays excellent efficiency with respect to hydrogen generation (690 ± 27.6 ?mol·h<sup>-1</sup>·g<sub>cat.</sub> <sup>-1</sup>), glucose conversion (~90%), and lactic acid selectivity (~87%) without any co-catalyst under visible light irradiation. The periodic WZ/ZB phase in twinning superlattice facilitates better charge separation, while superoxide radical (?O<sub>2</sub> <sup>-</sup>) and photogenerated holes drive the glucose transformation and water oxidation reactions, respectively. This work demonstrates that rational photocatalyst design could realize an efficient and concomitant production of hydrogen and value-added chemicals from glucose photocatalysis.
Project description:Research in solid-gas heterogeneous catalytic processes is typically aimed toward optimization of catalyst composition to achieve a higher conversion and, especially, a higher selectivity. However, even with the most selective catalysts, an upper limit is found: Above a certain temperature, gas-phase reactions become important and their effects cannot be neglected. Here, we apply a microwave field to a catalyst-support ensemble capable of direct microwave heating (MWH). We have taken extra precautions to ensure that (i) the solid phase is free from significant hot spots and (ii) an accurate estimation of both solid and gas temperatures is obtained. MWH allows operating with a catalyst that is significantly hotter than the surrounding gas, achieving a high conversion on the catalyst while reducing undesired homogeneous reactions. We demonstrate the concept with the CO2-mediated oxidative dehydrogenation of isobutane, but it can be applied to any system with significant undesired homogeneous contributions.
Project description:Titanium dioxide is the only known material that can enable gas-phase CO<sub>2</sub> photocatalysis in its anatase and rutile polymorphic forms. Materials engineering of polymorphism provides a useful strategy for optimizing the performance metrics of a photocatalyst. In this paper, it is shown that the less well known rhombohedral polymorph of indium sesquioxide, like its well-documented cubic polymorph, is a CO<sub>2</sub> hydrogenation photocatalyst for the production of CH<sub>3</sub>OH and CO. Significantly, the rhombohedral polymorph exhibits higher activity, superior stability and improved selectivity towards CH<sub>3</sub>OH over CO. These gains in catalyst performance originate in the enhanced acidity and basicity of surface frustrated Lewis pairs in the rhombohedral form.
Project description:Redox cocatalysts play crucial roles in photosynthetic reactions, yet simultaneous loading of oxidative and reductive cocatalysts often leads to enhanced charge recombination that is detrimental to photosynthesis. This study introduces an approach to simultaneously load two redox cocatalysts, atomically dispersed cobalt for improving oxidation activity and anthraquinone for improving reduction selectivity, onto graphitic carbon nitride (C3N4) nanosheets for photocatalytic H2O2 production. Spatial separation of oxidative and reductive cocatalysts was achieved on a two-dimensional (2D) photocatalyst, by coordinating cobalt single atom above the void center of C3N4 and anchoring anthraquinone at the edges of C3N4 nanosheets. Such spatial separation, experimentally confirmed and computationally simulated, was found to be critical for enhancing surface charge separation and achieving efficient H2O2 production. This center/edge strategy for spatial separation of cocatalysts may be applied on other 2D photocatalysts that are increasingly studied in photosynthetic reactions.
Project description:A precious metal and Cd-free photocatalyst system for efficient CO2 reduction in water is reported. The hybrid assembly consists of ligand-free ZnSe quantum dots (QDs) as a visible-light photosensitiser combined with a phosphonic acid-functionalised Ni(cyclam) catalyst, NiCycP. This precious metal-free photocatalyst system shows a high activity for aqueous CO2 reduction to CO (Ni-based TONCO > 120), whereas an anchor-free catalyst, Ni(cyclam)Cl2, produced three times less CO. Additional ZnSe surface modification with 2-(dimethylamino)ethanethiol (MEDA) partially suppresses H2 generation and enhances the CO production allowing for a Ni-based TONCO of > 280 and more than 33% selectivity for CO2 reduction over H2 evolution, after 20 h visible light irradiation (? > 400 nm, AM 1.5G, 1 sun). The external quantum efficiency of 3.4 ± 0.3% at 400 nm is comparable to state-of-the-art precious metal photocatalysts. Transient absorption spectroscopy showed that band-gap excitation of ZnSe QDs is followed by rapid hole scavenging and very fast electron trapping in ZnSe. The trapped electrons transfer to NiCycP on the ps timescale, explaining the high performance for photocatalytic CO2 reduction. With this work we introduce ZnSe QDs as an inexpensive and efficient visible light-absorber for solar fuel generation.
Project description:Cascade catalysis of reverse water gas shift (RWGS) and well-established CO hydrogenation holds promise for the conversion of greenhouse gas CO2 and renewable H2 into liquid hydrocarbons and methanol under mild conditions. However, it remains a big challenge to develop low-temperature RWGS catalysts with high activity, selectivity, and stability. Here, we report the design of an efficient RWGS catalyst by encapsulating ruthenium clusters with the size of 1 nm inside hollow silica shells. The spatially confined structure prevents the sintering of Ru clusters while the permeable silica layer allows the diffusion of gaseous reactants and products. This catalyst with reduced particle sizes not only inherits the excellent activity of Ru in CO2 hydrogenation reactions but also exhibits nearly 100% CO selectivity and superior stability at 200-500 °C. The ability to selectively produce CO from CO2 at relatively low temperatures paves the way for the production of value-added fuels from CO2 and renewable H2.
Project description:Thiourea (TU)/amine base cocatalysts are commonly employed for well-controlled, highly active "living" organocatalytic ring-opening polymerizations (ROPs) of cyclic esters and carbonates. In this work, several of the most active cocatalyst pairs are shown by (1)H NMR binding studies to be highly associated in solution, dominating all other known noncovalent catalyst/reagent interactions during ROP. One strongly binding catalyst pair behaves kinetically as a unimolecular catalyst species. The high selectivity and activity exhibited by these ROP organocatalysts are attributed to the strong binding between the two cocatalysts, and the predictive utility of these binding parameters is applied for the discovery of a new, highly active cocatalyst pair.