Boosting Interfacial Electron Transfer and CO2 Enrichment on ZIF-8/ZnTe for Selective Photoelectrochemical Reduction of CO2 to CO.

Artificial photosynthesis is an effective way of converting CO2 into fuel and high value-added chemicals. However, the sluggish interfacial electron transfer and adsorption of CO2 at the catalyst surface strongly hamper the activity and selectivity of CO2 reduction. Here, we report a photocathode attaching zeolitic imidazolate framework-8 (ZIF-8) onto a ZnTe surface to mimic an aquatic leaf featuring stoma and chlorophyll for efficient photoelectrochemical conversion of CO2 into CO. ZIF-8 possessing high CO2 adsorption capacity and diffusivity has been selected to enrich CO2 into nanocages and provide a large number of catalytic active sites. ZnTe with high light-absorption capacity serves as a light-absorbing layer. CO2 molecules are collected in large nanocages of ZIF-8 and delivered to the ZnTe surface. As evidenced by scanning electrochemical microscopy, the interface can effectively boost interfacial electron transfer kinetics. The ZIF-8/ZnTe photocathode with unsaturated Zn-Nx sites exhibits a high Faradaic efficiency for CO production of 92.9% and a large photocurrent of 6.67 mA·cm-2 at -2.48 V (vs Fc/Fc+) in a nonaqueous electrolyte at AM 1.5G solar irradiation (100 mW·cm-2).

Environment-Driven Variability in Absolute Band Edge Positions and Work Functions of Reduced Ceria.

The absolute band edge positions and work function (Φ) are the key electronic properties of metal oxides that determine their performance in electronic devices and photocatalysis. However, experimental measurements of these properties often show notable variations, and the mechanisms underlying these discrepancies remain inadequately understood. In this work, we focus on ceria (CeO2), a material renowned for its outstanding oxygen storage capacity, and combine theoretical and experimental techniques to demonstrate environmental modifications of its ionization potential (IP) and Φ. Under O-deficient conditions, reduced ceria exhibits a decreased IP and Φ with significant sensitivity to defect distributions. In contrast, the IP and Φ are elevated in O-rich conditions due to the formation of surface peroxide species. Surface adsorbates and impurities can further augment these variabilities under realistic conditions. We rationalize the shifts in energy levels by separating the individual contributions from bulk and surface factors, using hybrid quantum mechanical/molecular mechanical (QM/MM) embedded-cluster and periodic density functional theory (DFT) calculations supported by interatomic-potential-based electrostatic analyses. Our results highlight the critical role of on-site electrostatic potentials in determining the absolute energy levels in metal oxides, implying a dynamic evolution of band edges under catalytic conditions.

s valence electrons in cations of metal oxides serving as descriptors for electron and hole polarons.

In some metal oxides, an excess electron can give rise to the formation of a small polaron localized on a single site. However, there are still some metal oxides that exhibit the formation of a large polaron. The underlying mechanism behind this phenomenon remains unclear. In this study, we investigate polaron formation in metal oxides favorable for polaron formation using different functionals and through a review of the literature. Our findings indicate that the s valence electrons in cations could serve as a descriptor to classify the polarons in materials. In metal oxides with cations having ns (n ⩾ 5) valence electrons, excess charges trend to localize on several sites or form a two-dimensional shape, and even a large polaron, as these s electrons are delocalized in nature and have a large effect on p or d state polarons. The delocalized nature of ns (n ⩽ 4) valence electrons in cations is relatively small and does not affect the localization condition of p or d state polarons. Therefore, the excess charges in these metal oxides with ns (n ⩽ 4) valence electrons prefer to form a small polaron localizing on a single site. This work unveils the impact of the s valence in cations on polaron formation and provides a fundamental understanding of various types of polarons in metal oxides.

Oxygen evolution reaction (OER) active sites in BiVO4 studied using density functional theory and XPS experiments.

Bismuth vanadate (BiVO4/BVO) has been widely studied as a photocatalytic water splitting semiconductor material in recent years because of its many advantages, such as its ease of synthesis and suitable band gap (2.4 eV). However, BVO still has some disadvantages, one of which is the low photocatalytic water oxidation activity. It is intriguing and unexpected to note that in the current literature, Bi atoms are taken as the oxygen evolution reaction (OER) active sites, while V metal atoms are not investigated in the OER, and the underlying reason for this remains unknown. In this work, using density functional theory (DFT) calculations and ab initio molecular dynamics simulations, we found that in BVO, the VO4 tetrahedron structure is very stable and there is strong surface reconstruction that leads to the V atoms on the surface having the same coordinates as in the bulk. For some high index surfaces, there are some theoretically predicted unsaturated V sites, but it is very easy to form a VO4 tetrahedron structure again by taking oxygen atoms from water. The other intermediates of OER are difficult to adsorb or desorb on this VO4 structure, which makes the V sites in BVO unsuitable as OER active sites. This VO4 structure remained stable during the molecular dynamics simulation at 300 and 673 K. The XPS characterization of various BVO morphologies validates our primary findings from DFT and molecular dynamics simulations. It reveals the presence of unsaturated Bi sites on the BVO surface, while unsaturated V sites are not observed. This study provides novel insights into the enhancement of OER activity of BVO and offers a fundamental understanding of OER activity in other photocatalysts containing V atoms.

Bulk and Surface Contributions to Ionisation Potentials of Metal Oxides.

Determining the absolute band edge positions in solid materials is crucial for optimising their performance in wide-ranging applications including photocatalysis and electronic devices. However, obtaining absolute energies is challenging, as seen in CeO2 , where experimental measurements show substantial discrepancies in the ionisation potential (IP). Here, we have combined several theoretical approaches, from classical electrostatics to quantum mechanics, to elucidate the bulk and surface contributions to the IP of metal oxides. We have determined a theoretical bulk contribution to the IP of stoichiometric CeO2 of only 5.38 eV, while surface orientation results in intrinsic IP variations ranging from 4.2 eV to 8.2 eV. Highly tuneable IPs were also found in TiO2 , ZrO2 , and HfO2 , in which surface polarisation plays a pivotal role in long-range energy level shifting. Our analysis, in addition to rationalising the observed range of experimental results, provides a firm basis for future interpretations of experimental and computational studies of oxide band structures.

Polaron formation and transport in Bi2WO6 studied by DFT+U and hybrid PBE0 functional approaches.

Bi2WO6 (BWO) is considered as a promising material for photocatalytic water splitting. Its unique layered structure leads the charge separation, and transport is different from other materials. However, the charge transport mechanisms in BWO are not well understood. In this work, we investigated polaron formation and transport in BWO using the DFT+U and hybrid PBE0 functional approaches. We found that the electron will form 2-dimensional (2D)-shaped polarons among W sites in the ab plane of BWO with approximately 55% polaron density state on the central W site. This type of polaron is similar to the electron polarons in WO3. For other W-based materials, the electrons may also form a 2D-shaped polaron. We found that the W 6s orbital plays an important role in these 2D-shaped electron polarons. The calculated mobility of electron polarons in BWO was consistent with experimental findings. For the hole state, it could form a small hole polaron on the O site with O 2p in character. However, it will not form a polaron on the Bi site, which is quite different from BiVO4. This study provides insight for understanding polaron formation and transport in materials with W and Bi ions. It also provides understanding regarding charge separation and transport for materials with layered structures.

Theoretical insight into the anion vacancy healing process during the oxygen evolution reaction on TaON and Ta3N5.

Anion vacancies are common defects in materials, and they are usually much more stable on the outermost surface. These vacancies are sometimes taken as active sites in some reactions during catalysis. During the oxygen evolution reaction (OER), these vacancies may be healed by oxygen atoms from water. But this healing process is not well understood yet. In this work, we investigated the details of the anion vacancy healing process in the OER using TaON and Ta3N5 as models. In the OER process, we found that the vacancies are stable and cannot be healed without an applied potential. But with the equilibrium potential of 1.23 V, the vacancies on the outermost top surface will be healed. The oxygen vacancies, after healing, revert back to a clean surface. The nitrogen vacancies become an oxygen doped surface after vacancy healing. We also investigated the vacancy healing process on other well-known photocatalysts, like TiO2, BiVO4, WO3, α-Fe2O3, NaTaO3 and SrTiO3, and we found that the vacancies on the top surface of these materials will also be healed in the OER with an applied equilibrium potential of 1.23 V. The results presented here could expand to other materials used for the OER in (photo) electro-catalysis and photocatalysis. This work provides a new insight for understanding the role of vacancies in the OER.

The quantum size and spin-orbit coupling effects in BiVO4 with several atomic layers studied by density functional theory.

The quantum size and spin-orbit coupling (SOC) effects play an important role in the electronic structure of photocatalytic materials with heavy elements such as Bi, Pb, Ir, Te, Sb, Sn, etc. How these two effects affect the conduction band (CB) or the valence band (VB) edge of a photocatalyst is not well understood. In this work, we investigated the quantum size and SOC effects on the CB and VB edges of BiVO4 (BVO) with a thickness of several atomic layers. The BVO is a good water oxidation photocatalyst but doesn't have the hydrogen reduction ability. We find that when the thickness of a BVO layer is smaller than 0.64 nm, the CB edge upshifts significantly because of the quantum size effect. But after including the SOC effect, the CB edge remains almost unchanged. The CB edge of BVO upshifts above the equilibrium redox potentials for H2/H2O with a thickness of ∼0.64 to 1.28 nm. Within this thickness, only the quantum size effect dominates and the SOC effect is very weak. Both the quantum size and SOC effects are insignificant as the thickness of the BVO layers increases to be larger than 1.28 nm. The results presented here provide an essential step toward the understanding and rational design of photocatalysts from both the quantum size and SOC effects.

Charge Carrier Transport Mechanism in Ta2 O5 , TaON, and Ta3 N5 Studied by Applying Polaron Hopping and Bandlike Models.

TaON and Ta3 N5 are considered promising materials for photocatalytic and photoelectrochemical water splitting. In contrast, their counterpart Ta2 O5 does not exhibit good photocatalytic performance. This may be explained with the different charge carrier transport mechanisms in these materials, which are not well understood yet. Herein, we investigate the charge transport properties in Ta2 O5 , TaON, and Ta3 N5 by polaron hopping and bandlike models. First, the polaron binding energies were calculated to evaluate whether the small polaron occurs in these materials. Then we performed calculations to localize the excess carriers as small polarons using a hybrid density functional. We find that the small polaron hopping is the charge transfer mechanism in Ta2 O5, whereas our calculations indicate that this mechanism may not occur in TaON and Ta3 N5 . We also investigated the bandlike model mechanism by calculating the charge carrier mobility of these materials using the effective mass approximation, but the calculated mobility is not consistent with experimental results. This study is a first step towards understanding charge transport in oxynitrides and nitrides and furthermore establishes a simple rule to determine whether a small polaron occurs in a material.

On a high photocatalytic activity of high-noble alloys Au-Ag/TiO2 catalysts during oxygen evolution reaction of water oxidation.

The analysis via density functional theory was employed to understand high photocatalytic activity found on the Au-Ag high-noble alloys catalysts supported on rutile TiO2 during the oxygen evolution of water oxidation reaction (OER). It was indicated that the most thermodynamically stable location of the Au-Ag bimetal-support interface is the bridging row oxygen vacancy site. On the active region of the Au-Ag catalyst, the Au site is the most active for OER catalyzing the reaction with an overpotential of 0.60 V. Whereas the photocatalytic activity of other active sites follows the trend of Au > Ag > Ti. This finding evident from the projected density of states revealed the formation of the trap state that reduces the band gap of the catalyst promoting activity. In addition, the Bader charge analysis revealed the electron relocation from Ag to Au to be the reason behind the activity of the bimetallic that exceeds its monometallic counterparts.

Divergent Synthesis of Contorted Polycyclic Aromatics Containing Pentagons, Heptagon, and/or Azulene.

Divergent synthesis of four contorted aromatics containing pentagons, a heptagon, and/or an azulene from the same difluorenyl pentacenediene precursor were realized in one step. The subtle differences in molecular structure were confirmed by X-ray crystallography. The mechanisms for the control of different products, which involve a ring-expansion rearrangement, Scholl reactions, and/or Mallory cyclization were proposed on the basis of control experiments and DFT calculations. Such development adds good structure versatility and materials accessibility to the study of contorted aromatics.

Regio- and Steric Effects on Single Molecule Conductance of Phenanthrenes.

Here, six phenanthrene (the smallest arm-chair graphene nanoribbon) derivatives with dithiomethyl substitutions at different positions as the anchoring groups were synthesized. Scanning tunneling microscopy break junction technique was used to measure their single molecule conductances between gold electrodes, which showed a difference as much as 20-fold in the range of ∼10-2.82 G0 to ∼10-4.09 G0 following the trend of G2,7 > G3,6 > G2,6 > G1,7 > G1,6 > G1,8. DFT calculations agree well with this measured trend and indicate that the single molecule conductances are a combination of energy alignment, electronic coupling, and quantum effects. This significant regio- and steric effect on the single molecule conductance of phenanthrene model molecules shows the complexity in the practice of graphene nanoribbons as building blocks for future carbon-based electronics in one hand but also provides good conductance tunability on the other hand.

Bimetallic Mixed Clusters Highly Loaded on Porous 2D Graphdiyne for Hydrogen Energy Conversion.

There is no doubt that hydrogen energy can play significant role in promoting the development and progress of modern society. The utilization of hydrogen energy has developed rapidly, but it is far from the requirement of human. Therefore, it is very urgent to develop methodologies and technologies for efficient hydrogen production, especially high activity and durable electrocatalysts. Here a bimetallic oxide cluster on heterostructure of vanadium ruthenium oxides/graphdiyne (VRuOx /GDY) is reported. The unique acetylene-rich structure of graphdiyne achieves outstanding characteristics of electrocatalyst: i) controlled preparation of catalysts for achieving multiple-metal clusters; ii) regulation of catalyst composition and morphology for synthesizing high-performance catalysts; iii) highly active and durable hydrogen evolution reaction (HER) properties. The optimal porous electrocatalyst (VRu0.027 Ox /GDY) can deliver 10 mA cm-2 at low overpotentials of 13 and 12 mV together with robust long-term stability in alkaline and neutral media, respectively, which are much smaller than Pt/C. The results reveal that the synergism of different components can efficiently facilitate the electron/mass transport properties, reduce the energy barrier, and increase the active site number for high catalytic performances.

High Quality Pyrazinoquinoxaline-Based Graphdiyne for Efficient Gradient Storage of Lithium Ions.

N-doping of graphdiyne with atomic precision is very important for the study of heteroatom doping effect and the structure-properties relationships of graphdiyne. Here we report the bottom-up synthesis and characterizations of high-quality pyrazinoquinoxaline-based graphdiyne (PQ-GDY) film. First-principle studies of the layered structure were performed to examine the stacking mode, lithium binding affinity, and bulk lithium storage capacity. Three-stage insertion of 14 lithium atoms with binding affinities in the order of pyrazine nitrogen > diyne carbon > central aromatic ring were confirmed by both lithium-ion half-cell measurements and DFT calculations. More than half of the lithium atoms preferentially bind to pyrazine nitrogen, and a reversible capacity of 570.0 mA h g-1 at a current density of 200 mA g-1 after 800 cycles was achieved. Such a high capacity utilization rate of 97.2% provides a good case study of N-doped GDY with atomic precision.

Stringing the Perylene Diimide Bow.

This study explores a new mode of contortion in perylene diimides where the molecule is bent, like a bow, along its long axis. These bowed PDIs were synthesized through a facile fourfold Suzuki macrocyclization with aromatic linkers and a tetraborylated perylene diimide that introduces strain and results in a bowed structure. By altering the strings of the bow, the degree of bending can be controlled from flat to highly bent. Through spectroscopy and quantum chemical calculations, it is demonstrated that the energy of the lowest unoccupied orbital can be controlled by the degree of bending in the structures and that the energy of the highest occupied orbital can be controlled to a large extent by the constitution of the aromatic linkers. The important finding is that the bowing results not only in red-shifted absorptions but also more facile reductions.

Sr2NiWO6 Double Perovskite Oxide as a Novel Visible-Light-Responsive Water Oxidation Photocatalyst.

Screening of stable visible-light-responsive water oxidation semiconductor photocatalysts is highly desired for the development of photocatalytic water splitting systems. Herein, a visible-light-absorbing Sr2NiWO6 double perovskite oxide photocatalyst was successfully prepared via a conventional solid-state reaction method. The intrinsic Sr2NiWO6 shows photocatalytic oxygen evaluation reaction (OER) activity of 60 µmol h-1 g-1, even without loading any cocatalysts. The DFT calculation indicates that the Ni species on the surface is the active site for the OER. The photocatalytic OER activity was further improved by loading Pt and RuO2 dual redox cocatalysts on the surface of Sr2NiWO6 to achieve a photocatalytic OER activity of 420 µmol h-1 g-1, which corresponds to a remarkable apparent quantum efficiency (AQE) of 8.6% (λ ≈ 420 nm). The result indicates that Sr2NiWO6 is one of the best double perovskite oxide-based photocatalysts for the photocatalytic OER, and the activity is even comparable to the benchmark BiVO4-based photocatalyst. The improvement of the photocatalytic OER activity is due to the provision of more active redox sites as well as the synergetic effect of the dual redox cocatalysts in facilitating charge separation and transfer. This work demonstrates that double perovskite oxides may serve as a novel class of efficient and stable oxide-based semiconductor photocatalysts for water splitting.

Permethylation Introduces Destructive Quantum Interference in Saturated Silanes.

The single-molecule conductance of silanes is suppressed due to destructive quantum interference in conformations with cisoid dihedral angles along the molecular backbone. Yet, despite the structural similarity, σ-interference effects have not been observed in alkanes. Here we report that the methyl substituents used in silanes are a prerequisite for σ-interference in these systems. Through density functional theory calculations, we find that the destructive interference is not evident to the same extent in nonmethylated silanes. We find the same is true in alkanes as the transmission is significantly suppressed in permethylated cyclic and bicyclic alkanes. Using scanning tunneling microscope break-junction method we determine the single-molecule conductance of functionalized cyclohexane and bicyclo[2.2.2]octane that are found to be higher than that of equivalent permethylated silanes. Rather than the difference between carbon and silicon atoms in the molecular backbones, our calculations reveal that it is primarily the difference between hydrogen and methyl substituents that result in the different electron transport properties of nonmethylated alkanes and permethylated silanes. Chemical substituents play an important role in determining the single-molecule conductance of saturated molecules, and this must be considered when we improve and expand the chemical design of insulating organic molecules.

Controlling Singlet Fission by Molecular Contortion.

Singlet fission, the generation of two triplet excited states from the absorption of a single photon, may potentially increase solar energy conversion efficiency. A major roadblock in realizing this potential is the limited number of molecules available with high singlet fission yields and sufficient chemical stability. Here, we demonstrate a strategy for developing singlet fission materials in which we start with a stable molecular platform and use strain to tune the singlet and triplet energies. Using perylene diimide as a model system, we tune the singlet fission energetics from endoergic to exoergic or iso-energetic by straining the molecular backbone. The result is an increase in the singlet fission rate by 2 orders of magnitude. This demonstration opens a door to greatly expanding the molecular toolbox for singlet fission.