Yong Yan

Light-Driven Heterogeneous Reduction of Carbon Dioxide: Photocatalysts and Photoelectrodes

Photocatalysts and Photoelectrodes James L. White,† Maor F. Baruch,† James E. Pander III,† Yuan Hu,† Ivy C. Fortmeyer,† James Eujin Park,† Tao Zhang,† Kuo Liao,† Jing Gu,‡ Yong Yan,‡ Travis W. Shaw,† Esta Abelev,† and Andrew B. Bocarsly*,† †Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States ‡Chemical and Materials Science Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States

Low Surface Recombination Velocity in Solution-Grown CH3NH3PbBr3 Perovskite Single Crystal

Organic-inorganic hybrid perovskites are attracting intense research effort due to their impressive performance in solar cells. While the carrier transport parameters such as mobility and bulk carrier lifetime shows sufficient characteristics, the surface recombination, which can have major impact on the solar cell performance, has not been studied. Here we measure surface recombination dynamics in CH3NH3PbBr3 perovskite single crystals using broadband transient reflectance spectroscopy. The surface recombination velocity is found to be 3.4±0.1 × 103 cm s−1, ∼2–3 orders of magnitude lower than that in many important unpassivated semiconductors employed in solar cells. Our result suggests that the planar grain size for the perovskite thin films should be larger than ∼30 μm to avoid the influence of surface recombination on the effective carrier lifetime.

Electrochemistry of Aqueous Pyridinium: Exploration of a Key Aspect of Electrocatalytic Reduction of CO2 to Methanol

The mechanism by which pyridinium (pyrH(+)) is reduced at a Pt electrode is a matter of recent controversy. The quasireversible cyclic voltammetric wave observed at -0.58 V vs SCE at a Pt electrode was originally proposed to correspond to reduction of pyrH(+) to pyridinyl radical (pyrH(•)). This mechanistic explanation for the observed electrochemistry seems unlikely in light of recent quantum mechanical calculations that predict a very negative reduction potential (-1.37 V vs SCE) for the formation of pyrH(•). Several other mechanisms have been proposed to account for the discrepancy in calculated and observed reduction potentials, including surface adsorption of pyrH(•), reduction of pyrH(+) by two electrons rather than one, and reduction of the pyrH(+) proton to a surface hydride rather than a π-based radical product. This final mechanism, which can be described as inner-sphere reduction of pyrH(+) to form a surface hydride, is consistent with experimental observations.

Water reduction by a p-GaInP2 photoelectrode stabilized by an amorphous TiO2 coating and a molecular cobalt catalyst.

Producing hydrogen through solar water splitting requires the coverage of large land areas. Abundant metal-based molecular catalysts offer scalability, but only if they match noble metal activities. We report on a highly active p-GaInP2 photocathode protected through a 35-nm TiO2 layer functionalized by a cobaloxime molecular catalyst (GaInP2-TiO2-cobaloxime). This photoelectrode mediates H2 production with a current density of ∼9 mA cm(-2) at a potential of 0 V versus RHE under 1-sun illumination at pH 13. The calculated turnover number for the catalyst during a 20-h period is 139,000, with an average turnover frequency of 1.9 s(-1). Bare GaInP2 shows a rapid current decay, whereas the GaInP2-TiO2-cobaloxime electrode shows ≤5% loss over 20 min, comparable to a GaInP2-TiO2-Pt catalyst particle-modified interface. The activity and corrosion resistance of the GaInP2-TiO2-cobaloxime photocathode in basic solution is made possible by an atomic layer-deposited TiO2 and an attached cobaloxime catalyst.

p-Type CuRhO2 as a Self-Healing Photoelectrode for Water Reduction under Visible Light

Polycrystalline CuRhO2 is investigated as a photocathode for the splitting of water under visible irradiation. The band edge positions of this material straddle the water oxidation and reduction redox potentials. Thus, photogenerated conduction band electrons are sufficiently energetic to reduce water, while the associated valence band holes are energetically able to oxidize water to O2. Under visible illumination, H2 production is observed with ~0.2 V underpotential in an air-saturated solution. In contrast, H2 production in an Ar-saturated solution was found to be unstable. This instability is associated with the reduction of the semiconductor forming Cu(s). However, in the presence of air or O2, bulk Cu(s) was not detected, implying that CuRhO2 is self-healing when air is present. This property allows for the stable formation of H2 with ca. 80% Faradaic efficiency.

Monoanionic molybdenum and tungsten tris(dithiolene) complexes: a multifrequency EPR study.

Numerous Mo and W tris(dithiolene) complexes in varying redox states have been prepared and representative examples characterized crystallographically: [M(S(2)C(2)R(2))(3)](z) [M = Mo, R = Ph, z = 0 (1) or 1- (2); M = W, R = Ph, z = 0 (4) or 1- (5); R = CN, z = 2-, M = Mo (3) or W (6)]. Changes in dithiolene C-S and C-C bond lengths for 1 versus 2 and 4 versus 5 are indicative of ligand reduction. Trigonal twist angles (Θ) and dithiolene fold angles (α) increase and decrease, respectively, for 2 versus 1, 5 versus 4. Cyclic voltammetry reveals generally two reversible couples corresponding to 0/1- and 1-/2- reductions. The electronic structures of monoanionic molybdenum tris(dithiolene) complexes have been analyzed by multifrequency (S-, X-, Q-band) EPR spectroscopy. Spin-Hamiltonian parameters afforded by spectral simulation for each complex demonstrate the existence of two distinctive electronic structure types. The first is [Mo(IV)((A)L(3)(5-•))](1-) ((A)L = olefinic dithiolene, type A), which has the unpaired electron restricted to the tris(dithiolene) unit and is characterized by isotropic g-values and small molybdenum superhyperfine coupling. The second is formulated as [Mo(V)((B)L(3)(6-))](1-) ((B)L = aromatic dithiolene, type B) with spectra distinguished by a prominent g-anisotropy and hyperfine coupling consistent with the (d(z(2)))(1) paramagnet. The electronic structure disparity is also manifested in their electronic absorption spectra. The compound [W(bdt)(3)](1-) exhibits spin-Hamiltonian parameters similar to those of [Mo(bdt)(3)](1-) and thus is formulated as [W(V)((B)L(3)(6-))](1-). The EPR spectra of [W((A)L(3))](1-) display spin-Hamiltonian parameters that suggest their electronic structure is best represented by two resonance forms {[W(IV)((A)L(3)(5-•))](1-) ↔ [W(V)((A)L(3)(6-))](1-)}. The contrast with the corresponding [Mo(IV)((A)L(3)(5-•))](1-) complexes highlights tungstens preference for higher oxidation states.

Electronic Structure and Optical Properties of α-CH3NH3PbBr3 Perovskite Single Crystal

The electronic structure and related optical properties of an emerging thin-film photovoltaic material CH3NH3PbBr3 are studied. A block-shaped α-phase CH3NH3PbBr3 single crystal with the natural ⟨100⟩ surface is synthesized solvothermally. The room-temperature dielectric function ε = ε1 + iε2 spectrum of CH3NH3PbBr3 is determined by spectroscopic ellipsometry from 0.73 to 6.45 eV. Data are modeled with a series of Tauc-Lorentz oscillators, which show the absorption edge with a strong excitonic transition at ∼2.3 eV and several above-bandgap optical structures associated with the electronic interband transitions. The energy band structure and ε data of CH3NH3PbBr3 for the CH3NH3(+) molecules oriented in the ⟨111⟩ and ⟨100⟩ directions are obtained from first-principles calculations. The overall shape of ε data shows a qualitatively good agreement with experimental results. Electronic origins of major optical structures are discussed.

A graded catalytic–protective layer for an efficient and stable water-splitting photocathode

Solar water splitting is often performed in highly corrosive conditions, presenting materials stability challenges. Gu et al. show that an efficient and stable hydrogen-producing photocathode can be realized through the application of a graded catalytic–protective layer on top of the photoabsorber.

Computational studies on response and binding selectivity of fluorescence sensors.

Using a computational strategy based on density functional theory calculations, we successfully designed a fluorescent sensor for detecting Zn(2+) [J. Phys. Chem. B 2006, 110, 22991-22994]. In this work, we report our further studies on the computational design protocol for developing Photoinduced Electron Transfer (PET) fluorescence sensors. This protocol was applied to design a PET fluorescence sensor for Zn(2+) ions, which consists of anthracene as the fluorophore connected to pyridine as the receptor through dimethylethanamine as the linker. B3LYP and time-dependent B3LYP calculations were performed with the basis set 6-31G(d,p), 6-31+G(d,p), 6-311G(d,p), and 6-311+G(d,p). The calculated HOMO and LUMO energies of the fluorophore and receptor using all four basis sets show that the relative energy levels remain unchanged. This indicates that any of these basis sets can be used in calculating the relative molecular orbital (MO) energy levels. Furthermore, the relative MO energies of the independent fluorophore and receptor are not altered when they are linked together, which suggests that one can calculate the MO energies of these components separately and use them as the MO energies of the free sensor. These are promising outcomes for the computational design of sensors, though more case studies are needed to further confirm these conclusions. The binding selectivity studies indicate that the predicted sensor can be used for Zn(2+) even in the presence of the divalent cation, Ca(2+).

Ancillary Ligand Effects upon Dithiolene Redox Noninnocence in Tungsten Bis(dithiolene) Complexes

An expanded set of compounds of the type [W(S2C2Me2)2L1L2](n) (n = 0: L1 = L2 = CO, 1; L1 = L2 = CN(t)Bu, 2; L1 = CO, L2 = carbene, 3; L1 = CO, L2 = phosphine, 4; L1 = L2 = phosphine, 5. n = 2-: L1 = L2 = CN(-), [6](2-)) has been synthesized and characterized. Despite isoelectronic formulations, the compound set reveals gradations in the dithiolene ligand redox level as revealed by intraligand bond lengths, υ(CCchelate), and rising edge energies in the sulfur K-edge X-ray absorption spectra (XAS). Differences among the terminal series members, 1 and [6](2-), are comparable to differences seen in homoleptic dithiolene complexes related by full electron transfer to/from a dithiolene-based MO. The key feature governing these differences is the favorable energy of the CO π* orbitals, which are suitably positioned to overlap with tungsten d orbitals and exert an oxidizing effect on both metal and dithiolene ligand via π-backbonding. The CN(-) π* orbitals are too high in energy to mix effectively with tungsten and thus leave the filled dithiolene π* orbitals unperturbed. This work shows how, and the degree to which, the redox level of a noninnocent ligand can be modulated by the choice of ancillary ligands(s).