Experimental Demonstration of Topological Catalysis for CO2 Electroreduction.

The past decade has witnessed substantial progress in understanding nontrivial band topology and discovering exotic topological materials in condensed-matter physics. Recently, topological physics has been further extended to the chemistry discipline, leading to the emergence of topological catalysis. In principle, the topological effect is detectable in catalytic reactions, but no conclusive evidence has been reported yet. Herein, by precisely manipulating the topological surface state (TSS) of Bi2Se3 nanosheets through thickness control and the application of a magnetic field, we provide direct experimental evidence to illustrate topological catalysis for CO2 electroreduction. With and without the cooperation of TSS, CO2 is mainly reduced into liquid fuels (HCOOH and H2C2O4) and CO, exhibiting high (up to 90% at -1.1 V versus reversible hydrogen electrode) and low Faradaic efficiency (FE), respectively. Theoretically, the product and FE difference can be attributed to the TSS-regulated adsorption of key intermediates and the reduced barrier of the potential-determining step. Our work demonstrates the inherent correlation between band topology and electrocatalysis, paving a new avenue for designing high-performance catalysts.

Revealing Intramolecular Isotope Effects with Chemical-Bond Precision.

Isotope substitution of a molecule not only changes its vibrational frequencies but also changes its vibrational distributions in real-space. Quantitatively measuring the isotope effects inside a polyatomic molecule requires both energy and spatial resolutions at the single-bond level, which has been a long-lasting challenge in macroscopic techniques. By achieving ångström resolution in tip-enhanced Raman spectroscopy (TERS), we record the corresponding local vibrational modes of pentacene and its fully deuterated form, enabling us to identify and measure the isotope effect of each vibrational mode. The measured frequency ratio νH/νD varies from 1.02 to 1.33 in different vibrational modes, indicating different isotopic contributions of H/D atoms, which can be distinguished from TERS maps in real-space and well described by the potential energy distribution simulations. Our study demonstrates that TERS can serve as a non-destructive and highly sensitive methodology for isotope detection and recognition with chemical-bond precision.

Self-Limited Embedding Alternating 585-Ringed Divacancies and Metal Atoms into Graphene Nanoribbons.

Because of their theoretically predicted intriguing properties, it is interesting to embed periodic 585-ringed divacancies into graphene nanoribbons (GNRs), but it remains a great challenge. Here, we develop an on-surface cascade reaction from periodic hydrogenated divacancies to alternating 585-ringed divacancies and Ag atoms via intramolecular cyclodehydrogenation in a seven-carbon-wide armchair GNR on the Ag(111) surface. Combining scanning tunneling microscopy/spectroscopy and noncontact atomic force microscopy combined with first-principles calculations, we in-situ-monitor the evolution of the distinct structural and electronic properties in the reaction intermediates. The observation of embedded Ag atoms and further nudged elastic band calculations provide unambiguous evidence for Ag adatom-mediated C-H activation in the intramolecular cyclodehydrogenation pathway, where the strain-induced self-limiting effect contributes to the formation of the GNR superlattice with alternating 585-ringed divacancies and Ag atoms, which shows a band gap of about 1.4 eV. Our findings open an avenue to introducing periodic impurities of single metal atoms and nonhexagonal rings in on-surface synthesis, which may provide a novel route for multifunctional graphene nanostructures.

Remote-Triggered Domino-like Cyclodehydrogenation in Second-Layer Topological Graphene Nanoribbons.

Cyclodehydrogenation reactions in the on-surface synthesis of graphene nanoribbons (GNRs) usually involve a series of Csp2-Csp2 and/or Csp2-Csp3 couplings and just happen on uncovered metal or metal oxide surfaces. It is still a big challenge to extend the growth of second-layer GNRs in the absence of necessary catalytic sites. Here, we demonstrate the direct growth of topologically nontrivial GNRs via multistep Csp2-Csp2 and Csp2-Csp3 couplings in the second layer by annealing designed bowtie-shaped precursor molecules over one monolayer on the Au(111) surface. After annealing at 700 K, most of the polymerized chains that appear in the second layer covalently link to the first-layer GNRs that have partially undergone graphitization. Following annealing at 780 K, the second-layer GNRs are formed and linked to the first-layer GNRs. Benefiting from the minimized local steric hindrance of the precursors, we suggest that the second-layer GNRs undergo domino-like cyclodehydrogenation reactions that are remotely triggered at the link. We confirm the quasi-freestanding behaviors in the second-layer GNRs by measuring the quasiparticle energy gap of topological bands and the tunable Kondo resonance from topological end spins using scanning tunneling microscopy/spectroscopy combined with first-principles calculations. Our findings pave the avenue to diverse multilayer graphene nanostructures with designer quantum spins and topological states for quantum information science.

Hydrogen-Bond Network Promotes Water Splitting on the TiO2 Surface.

Breaking the strong covalent O-H bond of an isolated H2O molecule is difficult, but it can be largely facilitated when the H2O molecule is connected with others through hydrogen-bonding. How a hydrogen-bond network forms and performs becomes crucial for water splitting in natural photosynthesis and artificial photocatalysis and is awaiting a microscopic and spectroscopic understanding at the molecular level. At the prototypical photocatalytic H2O/anatase-TiO2(001)-(1×4) interface, we report the hydrogen-bond network can promote the coupled proton and hole transfer for water splitting. The formation of a hydrogen-bond network is controlled by precisely tuning the coverage of water to above one monolayer. Under ultraviolet (UV) light irradiation, the hydrogen-bond network opens a cascaded channel for the transfer of a photoexcited hole, concomitant with the release of the proton to form surface hydroxyl groups. The yielded hydroxyl groups provide excess electrons to the TiO2 surface, causing the reduction of Ti4+ to Ti3+ and leading to the emergence of gap states, as monitored by in situ UV/X-ray photoelectron spectroscopy. The density functional theory calculation reveals that the water splitting becomes an exothermic process through hole oxidation with the assistance of the hydrogen-bond network. In addition to the widely concerned exotic activity from photocatalysts, our study demonstrates the internal hydrogen-bond network, which is ubiquitous at practical aqueous/catalyst interfaces, is also indispensable for water splitting.

Formation of Plasmonic Polarons in Highly Electron-Doped Anatase TiO2.

The existence of various quasiparticles of polarons because of electron-boson couplings plays important roles in determining electron transport in titanium dioxide (TiO2), which affects a wealth of physical properties from catalysis to interfacial superconductivity. In addition to the well-defined Fröhlich polarons whose electrons are dressed by the phonon clouds, it has been theoretically predicted that electrons can also couple to their own plasmonic oscillations, namely, the plasmonic polarons. Here we experimentally demonstrate the formation of plasmonic polarons in highly doped anatase TiO2 using angle-resolved photoemission spectroscopy. Our results show that the energy separation of plasmon-loss satellites follows a dependence on √n, where n is the electron density, manifesting the characteristic of plasmonic polarons. The spectral functions enable to quantitatively evaluate the strengths of electron-plasmon and electron-phonon couplings, respectively, providing an effective approach for characterizing the interplays among different bosonic modes in the complicate many-body interactions.

Time- and momentum-resolved image-potential states of 2H-MoS2 surface.

Rydberg-like image potential states (IPSs) form special series surface states on metal and semiconducting surfaces. Here, using time-resolved and momentum-resolved multi-photon photoemission (mPPE), we measured the energy positions, band dispersion, and carrier lifetimes of IPSs at the 2H-MoS2 surface. The energy minima of the IPSs (n = 1 and 2) were located at 0.77 and 0.21 eV below the vacuum level. In addition, the effective masses of these two IPSs are close to the rest mass of the free electron, clearly showing nearly-free-electron character. These properties suggest a good screening effect in the MoS2 parallel to the surface. The multi-photon resonances between the valence band and IPS (n = 1) are observed, showing a k‖-momentum-dependent behavior. Our time-resolved mPPE measurements show that the lifetime of photoexcited electrons in the IPS (n = 1) is about 33 fs.

Interfacial Hydrogen-Bonding Dynamics in Surface-Facilitated Dehydrogenation of Water on TiO2(110).

Molecular-level understanding of the dehydrogenation of interfacial water molecules on metal oxides and their interactive nature relies on the ability to track the motion of light and small hydrogen atoms, which is known to be difficult. Here, we report precise measurements of the surface-facilitated water dehydrogenation process at terminal Ti sites of TiO2(110) using scanning tunneling microscopy. Our measured hydrogen-bond dynamics of H2O and D2O reveal that the vibrational and electronic excitations dominate the sequential transfer of two H (D) atoms from a H2O (D2O) molecule to adjacent surface oxygen sites, manifesting the active participation of the oxide surface in the dehydrogenation processes. Our results show that, at the stoichiometric Ti5c sites, individual H2O molecules are energetically less stable than the dissociative form, where a barrier is expected to be as small as approximately 70-120 meV on the basis of our experimental and theoretical results. Moreover, our results reveal that interfacial hydrogen bonds can effectively assist H atom transfer and exchange across the surface. The revealed quantitative hydrogen-bond dynamics provide a new atomistic mechanism for water interactions on metal oxides in general.

K Atom Promotion of O2 Chemisorption on Au(111) Surface.

Alkali atoms are known to promote or poison surface catalytic chemistry. To explore alkali promotion of catalysis and to characterize discharge species in alkali-oxygen batteries, we examine coadsorption of K and O2 on Au(111) surface at the atomic scale by scanning tunneling microscopy (STM) and density functional theory (DFT). On a clean Au(111) surface, O2 molecules may weakly physisorb, but when Au(111) is decorated with K+ ions, they chemisorb into structures that depend on the adsorbate concentrations and substrate templating. At low K coverages, an ordered quantum lattice of K2O2 complexes forms through intramolecular attractive and intermolecule repulsive interactions. For higher K and O2 coverages, the K2O2 complexes condense first into triangular islands, which further coalesce into rhombohedral islands, and ultimately into incommensurate films. No structures display internal contrast possibly because of high structural mutability. DFT calculations explain the alkali-promoted coadsorption in terms of three center, cation-π interactions where pairs of K+ coordinate the π-orbitals on each side of O2 molecules, and in addition O2 forms a covalent bond to Au(111) surface. The K promoted adsorption of O2 is catalyzed by charge transfer from K atoms to Au(111) substrate and ultimately to O2 molecules, forming O2-δ in a redox state between the peroxo and superoxo. Tunneling d I/d V spectra of K2O2 complexes exhibit inordinately intense inelastic progression involving excitation of the O-O stretching vibration, but absence of a Kondo effect suggests that the magnetic moment of O2 is quenched.

Coherent Electron Transfer at the Ag/Graphite Heterojunction Interface.

Charge transfer in transduction of light to electrical or chemical energy at heterojunctions of metals with semiconductors or semimetals is believed to occur by photogenerated hot electrons in metal undergoing incoherent internal photoemission through the heterojunction interface. Charge transfer, however, can also occur coherently by dipole coupling of electronic bands at the heterojunction interface. Microscopic physical insights into how transfer occurs can be elucidated by following the coherent polarization of the donor and acceptor states on the time scale of electronic dephasing. By time-resolved multiphoton photoemission spectroscopy (MPP), we investigate the coherent electron transfer from an interface state that forms upon chemisorption of Ag nanoclusters onto graphite to a σ symmetry interlayer band of graphite. Multidimensional MPP spectroscopy reveals a resonant two-photon transition, which dephases within 10 fs completing the coherent transfer.

Ultrafast Plasmon-Enhanced Hot Electron Generation at Ag Nanocluster/Graphite Heterojunctions.

Hot electron processes at metallic heterojunctions are central to optical-to-chemical or electrical energy transduction. Ultrafast nonlinear photoexcitation of graphite (Gr) has been shown to create hot thermalized electrons at temperatures corresponding to the solar photosphere in less than 25 fs. Plasmonic resonances in metallic nanoparticles are also known to efficiently generate hot electrons. Here we deposit Ag nanoclusters (NC) on Gr to study the ultrafast hot electron generation and dynamics in their plasmonic heterojunctions by means of time-resolved two-photon photoemission (2PP) spectroscopy. By tuning the wavelength of p-polarized femtosecond excitation pulses, we find an enhancement of 2PP yields by 2 orders of magnitude, which we attribute to excitation of a surface-normal Mie plasmon mode of Ag/Gr heterojunctions at 3.6 eV. The 2PP spectra include contributions from (i) coherent two-photon absorption of an occupied interface state (IFS) 0.2 eV below the Fermi level, which electronic structure calculations assign to chemisorption-induced charge transfer, and (ii) hot electrons in the π*-band of Gr, which are excited through the coherent screening response of the substrate. Ultrafast pump-probe measurements show that the IFS photoemission occurs via virtual intermediate states, whereas the characteristic lifetimes attribute the hot electrons to population of the π*-band of Gr via the plasmon dephasing. Our study directly probes the mechanisms for enhanced hot electron generation and decay in a model plasmonic heterojunction.

Unveiling diverse coordination-defined electronic structures of reconstructed anatase TiO2(001)-(1 × 4) surface.

Transition metal oxides (TMOs) exhibit fascinating physicochemical properties, which originate from the diverse coordination structures between the transition metal and oxygen atoms. Accurate determination of such structure-property relationships of TMOs requires to correlate structural and electronic properties by capturing the global parameters with high resolution in energy, real, and momentum spaces, but it is still challenging. Herein, we report the determination of characteristic electronic structures from diverse coordination environments on the prototypical anatase-TiO2(001) with (1 × 4) reconstruction, using high-resolution angle-resolved photoemission spectroscopy and scanning tunneling microscopy/atomic force microscopy, in combination with density functional theory calculation. We unveil that the shifted positions of O 2s and 2p levels and the gap-state Ti 3p levels can sensitively characterize the O and Ti coordination environments in the (1 × 4) reconstructed surface, which show distinguishable features from those in bulk. Our findings provide a paradigm to interrogate the intricate reconstruction-relevant properties in many other TMO surfaces.

Excitonic Effects of the Excited-State Photocatalytic Reaction at the Molecule/Metal Oxide Interface.

Excitonic effects caused by the Coulomb interaction between electrons and holes play a crucial role in photocatalysis at the molecule/metal oxide interface. As an ideal model for investigating the excitonic effect, coadsorption and photodissociation of water and methanol molecules on titanium dioxide involve complex ground-state thermalcatalytic and excited-state photocatalytic reaction processes. Herein, we systemically investigate the excited-state electronic structures of the coadsorption of H2O and CH3OH molecules on a rutile TiO2(110) surface by linear-response time-dependent density functional theory calculations and probe the reaction path for generating HCOOH or CO2, from ground-state and excited-state perspectives. The reaction barriers in excited-state calculations are significantly different from those in ground-state calculations during three processes, with the largest decrease being 0.94 eV for the Ti5c-O-CH2-O-Ti5c formation process.

Artificial kagome lattices of Shockley surface states patterned by halogen hydrogen-bonded organic frameworks.

Artificial electronic kagome lattices may emerge from electronic potential landscapes using customized structures with exotic supersymmetries, benefiting from the confinement of Shockley surface-state electrons on coinage metals, which offers a flexible approach to realizing intriguing quantum phases of matter that are highly desired but scarce in available kagome materials. Here, we devise a general strategy to construct varieties of electronic kagome lattices by utilizing the on-surface synthesis of halogen hydrogen-bonded organic frameworks (XHOFs). As a proof of concept, we demonstrate three XHOFs on Ag(111) and Au(111) surfaces, which correspondingly deliver regular, breathing, and chiral breathing diatomic-kagome lattices with patterned potential landscapes, showing evident topological edge states at the interfaces. The combination of scanning tunnelling microscopy and noncontact atomic force microscopy, complemented by density functional theory and tight-binding calculations, directly substantiates our method as a reliable and effective way to achieve electronic kagome lattices for engineering quantum states.

STM tip-assisted single molecule chemistry.

Scanning tunnelling microscopy (STM) has been a unique and powerful tool in the study of molecular systems among various microscopic and spectroscopic techniques. This benefits from the local probing ability for the atomically resolved structural and electronic characterization by the STM tip. Moreover, by using the STM tip one can modify a given structure and thus control the physical and chemical properties of molecules at a single-molecule level. The rapid developments in the past 30 years have extended the functions of STM far beyond characterization. It has shown the flexibility to combine STM with other techniques by making use of the advantages of the STM tip, demonstrating important applications in the growing nanotechnology. Here we review some recent progresses in our laboratory on single molecule chemistry by taking advantage of tip-assisted local approaches, such as the identification of specific orbitals or states of molecules on surfaces, tip-induced single-molecule manipulation, atomically resolved chemical reactions in photochemistry and tip-induced electroluminescence. We expect more joint techniques to emerge in the near future by using the unique advantages of STM tip, providing more powerful tools for the growing requirements of new materials design and the mechanism of chemical reactions at the molecular scale.

On-Surface Synthesis of Graphene Nanoribbons with Atomically Precise Structural Heterogeneities and On-Site Characterizations.

Graphene nanoribbons (GNRs) are strips of graphene, with widths of a few nanometers, that are promising candidates for future applications in nanodevices and quantum information processing due to their highly tunable structure-dependent electronic, spintronic, topological, and optical properties. Implantation of periodic structural heterogeneities, such as heteroatoms, nanopores, and non-hexagonal rings, has become a powerful manner for tailoring the designer properties of GNRs. The bottom-up synthesis approach, by combining on-surface chemical reactions based on rationally designed molecular precursors and in situ tip-based microscopic and spectroscopic techniques, promotes the construction of atomically precise GNRs with periodic structural modulations. However, there are still obstacles and challenges lying on the way toward the understanding of the intrinsic structure-property relations, such as the strong screening and Fermi level pinning effect of the normally used transition metal substrates and the lack of collective tip-based techniques that can cover multi-internal degrees of freedom of the GNRs. In this Perspective, we briefly review the recent progress in the on-surface synthesis of GNRs with diverse structural heterogeneities and highlight the structure-property relations as characterized by the noncontact atomic force microscopy and scanning tunneling microscopy/spectroscopy. We furthermore motivate to deliver the need for developing strategies to achieve quasi-freestanding GNRs and for exploiting multifunctional tip-based techniques to collectively probe the intrinsic properties.

Revealing the Polaron State at the MoS2/TiO2 Interface.

Interfacial polarons determine the distribution of free charges at the interface and thus play important roles in manipulating the physicochemical properties of hybridized polaronic materials. In this work, we investigated the electronic structures at the atomically flat interface of the single-layer MoS2 (SL-MoS2) on the rutile TiO2 surface using high-resolution angle-resolved photoemission spectroscopy. Our experiments directly visualized both the valence band maximum and the conduction band minimum (CBM) of SL-MoS2 at the K point, which clearly defines a direct bandgap of ∼2.0 eV. Detailed analyses corroborated by density functional theory calculations demonstrated that the CBM of MoS2 is formed by the trapped electrons at the MoS2/TiO2 interface that couple with the longitudinal optical phonons in the TiO2 substrate through an interfacial Fröhlich polaron state. Such an interfacial coupling effect may register a new route for tuning the free charges in the hybridized systems of two-dimensional materials and functional metal oxides.

Observation of photocatalytic dissociation of water on terminal Ti sites of TiO2(110)-1 × 1 surface.

The water splitting reaction based on the promising TiO(2) photocatalyst is one of the fundamental processes that bears significant implication in hydrogen energy technology and has been extensively studied. However, a long-standing puzzling question in understanding the reaction sequence of the water splitting is whether the initial reaction step is a photocatalytic process and how it happens. Here, using the low temperature scanning tunneling microscopy (STM) performed at 80 K, we observed the dissociation of individually adsorbed water molecules at the 5-fold coordinated Ti (Ti(5c)) sites of the reduced TiO(2) (110)-1 × 1 surface under the irradiation of UV lights with the wavelength shorter than 400 nm, or to say its energy larger than the band gap of 3.1 eV for the rutile TiO(2). This finding thus clearly suggests the involvement of a photocatalytic dissociation process that produces two kinds of hydroxyl species. One is always present at the adjacent bridging oxygen sites, that is, OH(br), and the other either occurs as OH(t) at Ti(5c) sites away from the original ones or even desorbs from the surface. In comparison, the tip-induced dissociation of the water can only produce OH(t) or oxygen adatoms exactly at the original Ti(5c) sites, without the trace of OH(br). Such a difference clearly indicates that the photocatalytic dissociation of the water undergoes a process that differs significantly from the attachment of electrons injected by the tip. Our results imply that the initial step of the water dissociation under the UV light irradiation may not be reduced by the electrons, but most likely oxidized by the holes generated by the photons.

Ultrafast charge transfer coupled to quantum proton motion at molecule/metal oxide interface.

Understanding how the nuclear quantum effects (NQEs) in the hydrogen bond (H-bond) network influence the photoexcited charge transfer at semiconductor/molecule interface is a challenging problem. By combining two kinds of emerging molecular dynamics methods at the ab initio level, the path integral-based molecular dynamics and time-dependent nonadiabatic molecular dynamics, and choosing CH3OH/TiO2 as a prototypical system to study, we find that the quantum proton motion in the H-bond network is strongly coupled with the ultrafast photoexcited charge dynamics at the interface. The hole trapping ability of the adsorbed methanol molecule is notably enhanced by the NQEs, and thus, it behaves as a hole scavenger on titanium dioxide. The critical role of the H-bond network is confirmed by in situ scanning tunneling microscope measurements with ultraviolet light illumination. It is concluded the quantum proton motion in the H-bond network plays a critical role in influencing the energy conversion efficiency based on photoexcitation.

Molecular oxygen adsorption behaviors on the rutile TiO2(110)-1×1 surface: an in situ study with low-temperature scanning tunneling microscopy.

A knowledge of adsorption behaviors of oxygen on the model system of the reduced rutile TiO(2)(110)-1×1 surface is of great importance for an atomistic understanding of many chemical processes. We present a scanning tunneling microcopy (STM) study on the adsorption of molecular oxygen either at the bridge-bonded oxygen vacancies (BBO(V)) or at the hydroxyls (OH) on the TiO(2)(110)-1×1 surface. Using an in situ O(2) dosing method, we are able to directly verify the exact adsorption sites and the dynamic behaviors of molecular O(2). Our experiments provide direct evidence that an O(2) molecule can intrinsically adsorb at both the BBO(V) and the OH sites. It has been identified that, at a low coverage of O(2), the singly adsorbed molecular O(2) at BBO(V) can be dissociated through an intermediate state as driven by the STM tip. However, singly adsorbed molecular O(2) at OH can survive from such a tip-induced effect, which implies that the singly adsorbed O(2) at OH is more stable than that at BBO(V). It is interesting to observe that when the BBO(V)s are fully filled with excess O(2) dosing, the adsorbed O(2) molecules at BBO(V) tend to be nondissociative even under a higher bias voltage of 2.2 V. Such a nondissociative behavior is most likely attributed to the presence of two or more O(2) molecules simultaneously adsorbed at a BBO(V) with a more stable configuration than singly adsorbed molecular O(2) at a BBO(V).