Nirala Singh

An autonomous photosynthetic device in which all charge carriers derive from surface plasmons

Solar conversion to electricity or to fuels based on electron-hole pair production in semiconductors is a highly evolved scientific and commercial enterprise. Recently, it has been posited that charge carriers either directly transferred from the plasmonic structure to a neighbouring semiconductor (such as TiO₂) or to a photocatalyst, or induced by energy transfer in a neighbouring medium, could augment photoconversion processes, potentially leading to an entire new paradigm in harvesting photons for practical use. The strong dependence of the wavelength at which the local surface plasmon can be excited on the nanostructure makes it possible, in principle, to design plasmonic devices that can harvest photons over the entire solar spectrum and beyond. So far, however, most such systems show rather small photocatalytic activity in the visible as compared with the ultraviolet. Here, we report an efficient, autonomous solar water-splitting device based on a gold nanorod array in which essentially all charge carriers involved in the oxidation and reduction steps arise from the hot electrons resulting from the excitation of surface plasmons in the nanostructured gold. Each nanorod functions without external wiring, producing 5 × 10(13) H₂ molecules per cm(2) per s under 1 sun illumination (AM 1.5 and 100 mW cm(-2)), with unprecedented long-term operational stability.

Particle suspension reactors and materials for solar-driven water splitting

Reactors based on particle suspensions for the capture, conversion, storage, and use of solar energy as H2 are projected to be cost-competitive with fossil fuels. In light of this, this review paper summarizes state-of-the-art particle light absorbers and cocatalysts as suspensions (photocatalysts) that demonstrate visible-light-driven water splitting on the laboratory scale. Also presented are reactor descriptions, theoretical considerations particular to particle suspension reactors, and efficiency and performance characterization metrics. Opportunities for targeted research, analysis, and development of reactor designs are highlighted.

Transition metal sulfide hydrogen evolution catalysts for hydrobromic acid electrolysis

Mixed metal sulfides containing combinations of W, Fe, Mo, Ni, and Ru were synthesized and screened for activity and stability for the hydrogen evolution reaction (HER) in aqueous hydrobromic acid (HBr). Co- and Ni-substituted RuS(2) were identified as potentially active HER electrocatalysts by high-throughput screening (HTS), and the specific compositions Co(0.4)Ru(0.6)S(2) and Ni(0.6)Ru(0.4)S(2) were identified by optimization. Hydrogen evolution activity of Co(0.4)Ru(0.6)S(2) in HBr is greater than RuS(2) or CoS(2) and comparable to Pt and commercial Rh(x)S(y). Structural and morphological characterizations of the Co-substituted RuS(2) suggest that the nanoparticulate solids are a homogeneous solid solution with a pyrite crystal structure. No phase separation is detected for Co substitutions below 30% by X-ray diffraction. In 0.5 M HBr electrolyte, the Co-Ru electrode material synthesized with 30% Co rapidly lost approximately 34% of the initial loading of Co; thereafter, it was observed to exhibit stable activity for HER with no further loss of Co. Density functional theory calculations indicate that the S(2)(2-) sites are the most important for HER and the presence of Co influences the S(2)(2-) sites such that the hydrogen binding energy at sufficiently high hydrogen coverage is decreased compared to ruthenium sulfide. Although showing high HER activity in a flow cell, the reverse reaction of hydrogen oxidation is slow on the RuS(2) catalysts tested when compared to platinum and rhodium sulfide, leaving rhodium sulfide as the only suitable tested material for a regenerative HBr cell due its stability compared to platinum.

Synthesis of chemicals using solar energy with stable photoelectrochemically active heterostructures.

Efficient and cost-effective conversion of solar energy to useful chemicals and fuels could lead to a significant reduction in fossil hydrocarbon use. Artificial systems that use solar energy to produce chemicals have been reported for more than a century. However the most efficient devices demonstrated, based on traditionally fabricated compound semiconductors, have extremely short working lifetimes due to photocorrosion by the electrolyte. Here we report a stable, scalable design and molecular level fabrication strategy to create photoelectrochemically active heterostructure (PAH) units consisting of an efficient semiconductor light absorber in contact with oxidation and reduction electrocatalysts and otherwise protected by alumina. The functional heterostructures are fabricated by layer-by-layer, template-directed, electrochemical synthesis in porous anodic aluminum oxide membranes to produce high density arrays of electronically autonomous, nanostructured, corrosion resistant, photoactive units (~10(9)-10(10) PAHs per cm(2)). Each PAH unit is isolated from its neighbor by the transparent electrically insulating oxide cellular enclosure that makes the overall assembly fault tolerant. When illuminated with visible light, the free floating devices have been demonstrated to produce hydrogen at a stable rate for over 24 h in corrosive hydroiodic acid electrolyte with light as the only input. The quantum efficiency (averaged over the solar spectrum) for absorbed photons-to-hydrogen conversion was 7.4% and solar-to-hydrogen energy efficiency of incident light was 0.9%. The fabrication approach is scalable for commercial manufacturing and readily adaptable to a variety of earth abundant semiconductors which might otherwise be unstable as photoelectrocatalysts.

Stable electrocatalysts for autonomous photoelectrolysis of hydrobromic acid using single-junction solar cells

Metal sulfides that are stable in bromine were investigated as electrocatalysts for hydrogen evolution in a photoelectrochemical device converting HBr to H2(g) and Br2(l). The photoanode was stabilized against photocorrosion using a poly(3,4-ethylenedioxythiophene) poly-(styrenesulfonate) (PEDOT:PSS) coating. Low loadings of rhodium sulfide nanoparticles were used as cathode electrocatalyst in place of platinum resulting in substantial improvement in the performance of a GaAs-based photosynthetic cell.

Investigation of the active sites of rhodium sulfide for hydrogen evolution/oxidation using carbon monoxide as a probe

Carbon monoxide (CO) was observed to decrease the activity for hydrogen evolution, hydrogen oxidation, and H2-D2 exchange on rhodium sulfide, platinum, and rhodium metal. The temperature at which the CO was desorbed from the catalyst surface (detected by recovery in the H2-D2 exchange activity of the catalyst) was used as a descriptor for the CO binding energy to the active site. The differences in the CO desorption temperature between the different catalysts showed that the rhodium sulfide active site is not metallic rhodium. Using density functional theory, the binding energy of CO to the Rh sites in rhodium sulfide is found comparable to the binding energy on Pt. Coupled with experiment this supports the proposition that rhodium rather than sulfur atoms in the rhodium sulfide are the active site for the hydrogen reaction. This would indicate the active sites for hydrogen evolution/oxidation as well as oxygen reduction (determined by other groups using X-ray absorption spectroscopy) may be the same.

Earth‐Abundant Tin Sulfide‐Based Photocathodes for Solar Hydrogen Production

Abstract Tin‐based chalcogenide semiconductors, though attractive materials for photovoltaics, have to date exhibited poor performance and stability for photoelectrochemical applications. Here, a novel strategy is reported to improve performance and stability of tin monosulfide (SnS) nanoplatelet thin films for H2 production in acidic media without any use of sacrificial reagent. P‐type SnS nanoplatelet films are coated with the n‐CdS buffer layer and the TiO2 passivation layer to form type II heterojunction photocathodes. These photocathodes with subsequent deposition of Pt nanoparticles generate a photovoltage of 300 mV and a photocurrent density of 2.4 mA cm−2 at 0 V versus reversible hydrogen electrode (RHE) for water splitting under simulated visible‐light illumination (λ > 500 nm, P in = 80 mW cm−2). The incident photon‐to‐current efficiency at 0 V versus RHE for H2 production reach a maximum of 12.7% at 575 nm with internal quantum efficiency of 13.8%. The faradaic efficiency for hydrogen evolution remains close to unity after 6000 s of illumination, confirming the robustness of the heterojunction for solar H2 production.