Zhongjie Huang

Photostable p-Type Dye-Sensitized Photoelectrochemical Cells for Water Reduction

A photostable p-type NiO photocathode based on a bifunctional cyclometalated ruthenium sensitizer and a cobaloxime catalyst has been created for visible-light-driven water reduction to produce H2. The sensitizer is anchored firmly on the surface of NiO, and the binding is resistant to the hydrolytic cleavage. The bifunctional sensitizer can also immobilize the water reduction catalyst. The resultant photoelectrode exhibits superior stability in aqueous solutions. Stable photocurrents have been observed over a period of hours. This finding is useful for addressing the degradation issue in dye-sensitized photoelectrochemical cells caused by desorption of dyes and catalysts. The high stability of our photocathodes should be important for the practical application of these devices for solar fuel production.

Linker effect in organic donor–acceptor dyes for p-type NiO dye sensitized solar cells

Three organic donor–acceptor dyes with different bridging ligands are reported for p-type NiO dye-sensitized solar cells (DSCs). The 3,4-ethoxythiophene linker outperforms thiophene and phenyl groups giving the best solar cell performance with Jsc = 1.74 mA cm−2, Voc = 90 mV, FF = 0.38, and an efficiency of 0.060%.

Aqueous Lithium–Iodine Solar Flow Battery for the Simultaneous Conversion and Storage of Solar Energy

Integrating both photoelectric-conversion and energy-storage functions into one device allows for the more efficient solar energy usage. Here we demonstrate the concept of an aqueous lithium-iodine (Li-I) solar flow battery (SFB) by incorporation of a built-in dye-sensitized TiO2 photoelectrode in a Li-I redox flow battery via linkage of an I3(-)/I(-) based catholyte, for the simultaneous conversion and storage of solar energy. During the photoassisted charging process, I(-) ions are photoelectrochemically oxidized to I3(-), harvesting solar energy and storing it as chemical energy. The Li-I SFB can be charged at a voltage of 2.90 V under 1 sun AM 1.5 illumination, which is lower than its discharging voltage of 3.30 V. The charging voltage reduction translates to energy savings of close to 20% compared to conventional Li-I batteries. This concept also serves as a guiding design that can be extended to other metal-redox flow battery systems.

Dimeric [Mo2S12]2− Cluster: A Molecular Analogue of MoS2 Edges for Superior Hydrogen‐Evolution Electrocatalysis

Proton reduction is one of the most fundamental and important reactions in nature. MoS2 edges have been identified as the active sites for hydrogen evolution reaction (HER) electrocatalysis. Designing molecular mimics of MoS2 edge sites is an attractive strategy to understand the underlying catalytic mechanism of different edge sites and improve their activities. Herein we report a dimeric molecular analogue [Mo2 S12 ](2-) , as the smallest unit possessing both the terminal and bridging disulfide ligands. Our electrochemical tests show that [Mo2 S12 ](2-) is a superior heterogeneous HER catalyst under acidic conditions. Computations suggest that the bridging disulfide ligand of [Mo2 S12 ](2-) exhibits a hydrogen adsorption free energy near zero (-0.05 eV). This work helps shed light on the rational design of HER catalysts and biomimetics of hydrogen-evolving enzymes.

Membrane-Inspired Acidically Stable Dye-Sensitized Photocathode for Solar Fuel Production

Tandem dye-sensitized photoelectrochemical cells (DSPECs) for water splitting are a promising method for sustainable energy conversion but so far have been limited by their lack of aqueous stability and photocurrent mismatch between the cathode and anode. In nature, membrane-enabled subcellular compartmentation is a general approach to control local chemical environments in the cell. The hydrophobic tails of the lipid make the bilayer impermeable to ions and hydrophilic molecules. Herein we report the use of an organic donor-acceptor dye that prevents both dye desorption and semiconductor degradation by mimicking the hydrophobic/hydrophilic properties of lipid bilayer membranes. The dual-functional photosensitizer (denoted as BH4) allows for efficient light harvesting while also protecting the semiconductor surface from protons and water via its hydrophobic π linker. The protection afforded by this membrane-mimicking dye gives this system excellent stability in extremely acidic (pH 0) conditions. The acidic stability also allows for the use of cubane molybdenum-sulfide cluster as the hydrogen evolution reaction (HER) catalyst. This system produces a proton-reducing current of 183 ± 36 μA/cm(2) (0 V vs NHE with 300 W Xe lamp) for an unprecedented 16 h with no degradation. These results introduce a method for developing high-current, low-pH DSPECs and are a significant move toward practical dye-sensitized solar fuel production.

Valence Band-Edge Engineering of Nickel Oxide Nanoparticles via Cobalt Doping for Application in p-Type Dye-Sensitized Solar Cells

We have systematically studied the effects of substitutional doping of p-type nanoparticulate NiO with cobalt ions. Thin films of pure and Co-doped NiO nanoparticles with nominal compositions Co(x)Ni(1-x)O(y) (0 ≤ x ≤ 0.1) were fabricated using sol-gel method. X-ray photoelectron spectroscopy revealed a surface enrichment of divalent cobalt ions in the Co(x)Ni(1-x)O(y) nanoparticles. Mott-Schottky analysis in aqueous solutions was used to determine the space charge capacitance values of the films against aqueous electrolytes, which yielded acceptor state densities (N(A)) and apparent flat-band potentials (E(fb)). Both N(A) and E(fb) values of the doped NiO were found to gradually increase with increasing amount of doping; thus the Fermi energy level of the charge carriers decreased with Co-doping. The photovoltage of p-DSCs constructed using the Co(x)Ni(1-x)O(y) films increased with increasing amount of cobalt, as expected from the trend in the E(fb). Co-doping increased both carrier lifetimes within the p-DSCs and the carrier transport times within the nanoparticulate semiconductor network. The nominal composition of Co₀.₀₆Ni₀.₉₄O(y) was found to be optimal for use in p-DSCs.

Solar-powered electrochemical energy storage: an alternative to solar fuels

Because of the intermittent nature of solar radiation, being able to simultaneously convert and store solar energy is a significant advance for efficiently harnessing solar energy. Solar fuels have already been recognized as a promising method towards this goal and have attracted tremendous research interest recently. Alternatively, this goal can also be achieved by using the solar-powered electrochemical energy storage (SPEES) strategy, which integrates a photoelectrochemical cell and an electrochemical cell into a single device. The integrated device is able to harvest solar energy and store it in situ within the device via a photocharging process and also distribute the energy as electric power when needed. This essay reviews the past SPEES research and analyzes its future prospects with a special emphasis on chemical design and material choices. We hope that the article will help draw more research attention to this field and stimulate additional exciting investigations toward more efficient solar energy utilization.

The effect of an atomically deposited layer of alumina on NiO in P-type dye-sensitized solar cells.

We present a systematic investigation of the fundamental effects of an atomically deposited alumina (AlO(x)H(y)) onto the NiO films in p-type dye-sensitized solar cells (p-DSCs). With P1 as the sensitizing dye and 0.1 M I(2) and 1.0 M LiI in 3-methoxypropionitrile as the electrolyte, one atomic layer deposition (ALD) cycle of alumina was used to achieve a 74% increase in the overall conversion efficiency of a NiO-based DSC. The open circuit voltage of the cells increased from 0.11 to 0.15 V, and the short circuit current density increased from 0.83 to 0.95 mA/cm(2). Adsorption isotherm studies were performed to show that the amount of dye adsorbed on the NiO-alumina film is slightly lower than the amount adsorbed on the nontreated NiO film. The increased J(sc) was therefore assigned to the increased efficiency of carrier collection at the semiconductor-FTO interface. Our study of the photocurrent onset potentials of NiO and NiO-alumina films with the chopped light measurement technique showed no definitive difference in the onset potential values. However, the DSCs based on NiO-alumina showed a higher recombination resistance value from the electrochemical impedance studies and a higher diode ideality factor from the V(oc) versus ln(light intensity) plots as compared to the DSCs based on untreated NiO. It has thus been established that the increase in V(oc) upon alumina treatment arises due to a higher resistance for electron-hole recombination across NiO surface locally.

Dye-controlled interfacial electron transfer for high-current indium tin oxide photocathodes.

Efficient sensitized photocathodes are highly desired for solar fuels and tandem solar cells, yet the development is hindered by the scarcity of suitable p-type semiconductors. The generation of high cathodic photocurrents by sensitizing a degenerate n-type semiconductor (tin-doped indium oxide; ITO) is reported. The sensitized mesoporous ITO electrodes deliver cathodic photocurrents of up to 5.96±0.19 mA cm(-2), which are close to the highest record in conventional p-type sensitized photocathodes. This is realized by the rational selection of dyes with appropriate energy alignments with ITO. The energy level alignment between the highest occupied molecular orbital of the sensitizer and the conduction band of ITO is crucial for efficient hole injection. Transient absorption spectroscopy studies demonstrate that the cathodic photocurrent results from reduction of the photoexcited sensitizer by free electrons in ITO. Our results reveal a new perspective toward the selection of electrode materials for sensitized photocathodes.

Tunable Molecular MoS2 Edge-Site Mimics for Catalytic Hydrogen Production

Molybdenum sulfides represent state-of-the-art, non-platinum electrocatalysts for the hydrogen evolution reaction (HER). According to the Sabatier principle, the hydrogen binding strength to the edge active sites should be neither too strong nor too weak. Therefore, it is of interest to develop a molecular motif that mimics the catalytic sites structurally and possesses tunable electronic properties that influence the hydrogen binding strength. Furthermore, molecular mimics will be important for providing mechanistic insight toward the HER with molybdenum sulfide catalysts. In this work, a modular method to tune the catalytic properties of the S-S bond in MoO(S2)2L2 complexes is described. We studied the homogeneous electrocatalytic hydrogen production performance metrics of three catalysts with different bipyridine substitutions. By varying the electron-donating abilities, we present the first demonstration of using the ligand to tune the catalytic properties of the S-S bond in molecular MoS2 edge-site mimics. This work can shed light on the relationship between the structure and electrocatalytic activity of molecular MoS2 catalysts and thus is of broad importance from catalytic hydrogen production to biological enzyme functions.