2.3. Evaluation of Photocatalytic Water Splitting 6507 2.3.1. Photocatalytic Activity 6507 2.3.2. Photocatalytic Stability 6507 3. UV-Active Photocatalysts for Water Splitting 6507 3.1. d0 Metal Oxide Photocatalyts 6507 3.1.1. Ti-, Zr-Based Oxides 6507 3.1.2. Nb-, Ta-Based Oxides 6514 3.1.3. W-, Mo-Based Oxides 6517 3.1.4. Other d0 Metal Oxides 6518 3.2. d10 Metal Oxide Photocatalyts 6518 3.3. f0 Metal Oxide Photocatalysts 6518 3.4. Nonoxide Photocatalysts 6518 4. Approaches to Modifying the Electronic Band Structure for Visible-Light Harvesting 6519

Semiconductor-based Photocatalytic Hydrogen Generation

Annals of physics

In this Review, we discuss the state-of-the-art understanding of non-precious transition metal oxides that catalyze the oxygen reduction and evolution reactions. Understanding and mastering the kinetics of oxygen electrocatalysis is instrumental to making use of photosynthesis, advancing solar fuels, fuel cells, electrolyzers, and metal–air batteries. We first present key insights, assumptions and limitations of well-known activity descriptors and reaction mechanisms in the past four decades. The turnover frequency of crystalline oxides as promising catalysts is also put into perspective with amorphous oxides and photosystem II. Particular attention is paid to electronic structure parameters that can potentially govern the adsorbate binding strength and thus provide simple rationales and design principles to predict new catalyst chemistries with enhanced activity. We share new perspective synthesizing mechanism and electronic descriptors developed from both molecular orbital and solid state band structure principles. We conclude with an outlook on the opportunities in future research within this rapidly developing field.

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Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis

The electrocatalytic hydrogen-evolution reaction (HER), as the main step of water splitting and the cornerstone of exploring the mechanism of other multi-electron transfer electrochemical processes, is the subject of extensive studies. A large number of high-performance electrocatalysts have been developed for HER accompanied by recent significant advances in exploring its electrochemical nature. Herein we present a critical appraisal of both theoretical and experimental studies of HER electrocatalysts with special emphasis on the electronic structure, surface (electro)chemistry, and molecular design. It addresses the importance of correlating theoretical calculations and electrochemical measurements toward better understanding of HER electrocatalysis at the atomic level. Fundamental concepts in the computational quantum chemistry and its relation to experimental electrochemistry are also presented along with some featured examples.

Advancing the Electrochemistry of the Hydrogen-Evolution Reaction through Combining Experiment and Theory

With rapid progress in a power conversion efficiency (PCE) to reach 25%, metal halide perovskite-based solar cells became a game-changer in a photovoltaic performance race. Triggered by the development of the solid-state perovskite solar cell in 2012, intense follow-up research works on structure design, materials chemistry, process engineering, and device physics have contributed to the revolutionary evolution of the solid-state perovskite solar cell to be a strong candidate for a next-generation solar energy harvester. The high efficiency in combination with the low cost of materials and processes are the selling points of this cell over commercial silicon or other organic and inorganic solar cells. The characteristic features of perovskite materials may enable further advancement of the PCE beyond those afforded by the silicon solar cells, toward the Shockley-Queisser limit. This review summarizes the fundamentals behind the optoelectronic properties of perovskite materials, as well as the important approaches to fabricating high-efficiency perovskite solar cells. Furthermore, possible next-generation strategies for enhancing the PCE over the Shockley-Queisser limit are discussed.

High-Efficiency Perovskite Solar Cells.

Record Open-Circuit Voltage Wide-Bandgap Perovskite Solar Cells Utilizing 2D/3D Perovskite Heterostructure

By combining ultraviolet and x-ray photoelectron spectroscopy with inverse photoemission spectroscopy, we find that the conduction-band alignment at the CdS/CuInSe2 thin-film solar-cell heterojunction is flat (0.0±0.2 eV). Furthermore, we observe a valence-band offset of 0.8±0.2 eV. The electronic level alignment is dominated by (1) an unusually large surface band gap of the CuInSe2 thin film (1.4 eV), (2) by a reduced surface band gap of the CdS overlayer (2.2 eV) due to intermixing effects, and (3) by a general influence of the intermixing on the chemical state near the interface.

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Flat conduction-band alignment at the CdS/CuInSe2 thin-film solar-cell heterojunction

The electronic structure of the CdS/Cu2ZnSnS4 (CZTS) heterojunction was investigated by direct and inverse photoemission. The effects of a KCN etch of the CZTS absorber prior to CdS deposition on the band alignment at the respective interface were studied. We find a “cliff”-like conduction band offset at the CdS/CZTS interface independent of absorber pretreatment and a significant etch-induced enhancement of the energetic barrier for charge carrier recombination across the CdS/CZTS interface.

Cliff-like conduction band offset and KCN-induced recombination barrier enhancement at the CdS/Cu2ZnSnS4 thin-film solar cell heterojunction

Polycrystalline WO3 thin films for photoelectrochemical hydrogen production were investigated using photoelectron spectroscopy and inverse photoemission. First, we report on a careful study to mini...

Electronic Surface Level Positions of WO3 Thin Films for Photoelectrochemical Hydrogen Production

High-resolution x-ray absorption and emission spectra of liquid water exhibit a strong isotope effect. Further, the emission spectra show a splitting of the 1b1 emission line, a weak temperature effect, and a pronounced excitation-energy dependence. They can be described as a superposition of two independent contributions. By comparing with gas phase, ice, and NaOH/NaOD, we propose that the two components are governed by the initial state hydrogen bonding configuration and ultrafast dissociation on the time scale of the O 1s core hole decay.

Lothar Weinhardt

Papers

Record Open-Circuit Voltage Wide-Bandgap Perovskite Solar Cells Utilizing 2D/3D Perovskite Heterostructure

Flat conduction-band alignment at the CdS/CuInSe2 thin-film solar-cell heterojunction

Cliff-like conduction band offset and KCN-induced recombination barrier enhancement at the CdS/Cu2ZnSnS4 thin-film solar cell heterojunction

Electronic Surface Level Positions of WO3 Thin Films for Photoelectrochemical Hydrogen Production

Isotope and temperature effects in liquid water probed by x-ray absorption and resonant x-ray emission spectroscopy