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Liquid methanol has the potential to be the hydrogen energy carrier and storage medium for the future green economy. However, there are still many challenges before zero-emission, affordable molecular H 2 can be extracted from methanol with high performance. Here, we present noble-metal-free Cu–WC/W plasmonic nanohybrids which exhibit unsurpassed solar H 2 extraction efficiency from pure methanol of 2,176.7 µmol g −1 h −1 at room temperature and normal pressure. Macro-to-micro experiments and simulations unveil that local reaction microenvironments are generated by the coperturbation of WC/W’s lattice strain and infrared-plasmonic electric field. It enables spontaneous but selective zero-emission reaction pathways. Such microenvironments are found to be highly cooperative with solar-broadband-plasmon-excited charge carriers flowing from Cu to WC surfaces for efficient stable CH 3 OH plasmonic reforming with C 3 -dominated liquid products and 100% selective gaseous H 2 . Such high efficiency, without any CO x emission, can be sustained for over a thousand-hour operation without obvious degradation.

Owing to its inherent non-trivial geometry, the unique structural motif of the recently discovered kagome topological superconductor AV

Impurity doping is a viable route toward achieving desired subgap optical response in semiconductors. In strongly excitonic two-dimensional (2D) semiconductors such as transition metal dichalcogenides (TMDs), impurities are expected to result in bound-exciton emission. However, doped TMDs often exhibit a broad Stokes-shifted emission without characteristic features, hampering strategic materials engineering. Here we report observation of a well-defined impurity-induced emission in monolayer WS2 substitutionally doped with rhenium (Re), which is an electron donor. The emission exhibits characteristics of localized states and dominates the spectrum up to 200 K. Gate dependence reveals that neutral impurity centers are responsible for the observed emission. Using GW-Bethe-Salpeter equation (GW-BSE) calculations, we attribute the emission to transitions between spin-split upper Re band and valence band edge.

Epitaxial growth is a powerful tool for synthesizing heterostructures and integrating multiple functionalities. However, interfacial mixing can readily occur and significantly modify the properties of layered structures, particularly for those containing energy storage materials with smaller cations. Here, we show a two-step sequence involving the growth of an epitaxial LiCoO

An atomically dispersed structure is attractive for electrochemically converting carbon dioxide (CO2) to fuels and feedstock due to its unique properties and activity. Most single-atom electrocatalysts are reported to reduce CO2 to carbon monoxide (CO). Herein, we develop atomically dispersed indium (In) on a nitrogen-doped carbon skeleton (In-N-C) as an efficient catalyst to produce formic acid/formate in aqueous media, reaching a turnover frequency as high as 26771 h-1 at -0.99 V relative to a reversible hydrogen electrode (RHE). Electrochemical measurements show that trace amounts of In loaded on the carbon matrix significantly improve the electrocatalytic behavior for the CO2 reduction reaction, outperforming conventional metallic In catalysts. Further experiments and density functional theory (DFT) calculations reveal that the formation of intermediate *OCHO on isolated In sites plays a pivotal role in the efficiency of the CO2-to-formate process, which has a lower energy barrier than that on metallic In.

The advent of two-dimensional transition metal dichalcogenides (2D-TMDs) has led to an extensive amount of interest amongst scientists and engineers alike and an intensive amount of research has brought about major breakthroughs in the electronic and optical properties of 2D materials. This in turn has generated considerable interest in novel device applications. With the polymorphic structural features of 2D-TMDs, this class of materials can exhibit both semiconducting and metallic (quasi-metallic) properties in their respective phases. This polymorphic property further increases the interest in 2D-TMDs both in fundamental research and for their potential utilization in novel high-performance device applications. In this review, we highlight the unique structural properties of few-layer and monolayer TMDs in the metallic 1T- and quasi-metallic 1T'-phases, and how these phases dictate their electronic and optical properties. An overview of the semiconducting-to-(quasi)-metallic phase transition of 2D-TMD systems will be covered along with a discussion on the phase transition mechanisms. The current development in the applications of (quasi)-metallic 2D-TMDs will be presented ranging from high-performance electronic and optoelectronic devices to energy storage, catalysis, piezoelectric and thermoelectric devices, and topological insulator and neuromorphic computing applications. We conclude our review by highlighting the challenges confronting the utilization of TMD-based systems and projecting the future developmental trends with an outlook of the progress needed to propel this exciting field forward.

Epitaxial Fe3O4 thin films grown on single crystal MgO(001) present well-defined model systems to study fundamental multivalent ion diffusion and associated phase transition processes in transition...

Recently, considerable interest in the fields of photovoltaics, light emission, and photodetection absorbers has centered on hybrid organic–inorganic perovskites (HOIPs). Here, we report a combined...

Hybrid organic-inorganic perovskites (HOIPs) have emerged to the forefront of optoelectronic material advancements for the past few years. However, our understanding on electronic structure and correlations are still lacking. Herewith, by simultaneously analyzing complex dielectric function, loss functions, and reflectivity directly obtained from spectroscopic ellipsometry and supported with theoretical calculations, we report new spin correlated-plasmons with low loss in (MA)2CuCl4. Photoluminescence and time-resolved photoluminescence measurements show a broadband emission band originating from the self-trapped emission excitons. Through X-ray absorption spectroscopy and resonant photoemission spectroscopy measurements at the C K-edge, a resonance enhancement peak is observed and unravels a charge transfer event due to the opening of an extra autoionization channel. Our result shows the importance of coupling between spin correlated-plasmons and electron-hole pairs together with spin-dependent exchange interaction in determining electronic structure and optical properties of HOIPS. Ministry of Education (MOE) National Research Foundation (NRF) This work is supported by the Singapore Ministry of Education (MOE) AcRF Tier-2 (MOE2017 T2-1-135, MOE2018-T2-1- 088, MOE2018-T2-2-117, and MOE2019-T2-1-163), MOE AcRF Tier-3 (MOE2014-T3-1-004), MOE-AcRF Tier-1 (R144-000-423-114, R-144-000-398-114, R-144-000-379-114 and R-144-000-368-112), the Singapore National Research Foundation under its Competitive Research Funding (No. R-398-000- 087-281) and under its Medium Sized Centre Program (Centre for Advanced 2D Materials and Graphene Research Centre), NUS YIA, and the 2015 PHC Merlion Project. NTU authors acknowledge the MOE-AcRF Tier-2 (MOE2016-T2-1-052). The authors acknowledge the Singapore Synchrotron Light Source (SSLS) for providing the facility necessary for conducting the research. The Laboratory is a National Research Infrastructure under the National Research Foundation Singapore.

Enhancing catalytic activity by decorating noble metals in catalysts provides an opportunity for promoting the electrocatalytic hydrogen evolution reaction (HER) application. However, there are few...

Well-defined heterointerface formation between low bandgap π-conjugated organic materials and all-inorganic perovskites is desirable for the advancement of physical, chemical, and electronic interactions in solar-cell devices. Herein, we investigate the charge carrier dynamics and optical responses across three representative functionalized-heptazetherene molecules on CsPbBr3 thin films using synchrotron high-resolution photoemission techniques, namely, X-ray photoemission spectroscopy, X-ray absorption spectroscopy, resonant photoemission spectroscopy and photoluminescence spectroscopy. Chemical substitution on the heptazethrene backbone results in tunable formation of interfacial dipoles at the heptazethrene/CsPbBr3 interfaces. Charge transfer across these interfaces is enhanced by the presence of highly electronegative fluorine atoms or electron-donating alkyl-based chain groups in the molecular periphery. Resonant valence spectra near the K-edge threshold indicate that the core-decay participator channel contributes to the charge transfer dynamics with an average charge transfer time of ∼12 fs. First-principles calculations indicated that the charge transfer across the molecule/perovskite interfaces can be modulated via chemical design. In addition, we observe that the photoluminesence quenching of the perovskite and the molecule signals can be attributed to the efficent energy transfer across the interface. This work systematically addresses the potential of functionalized-zethrene molecules as active materials for ultra-thin hybrid solar cell devices.

We report the observation of superconductivity in infinite-layer Ca-doped LaNiO

A controllable electronic manipulation in a frustrated magnetic system such as solution-based two-dimensional (2D) all-inorganic perovskites offers a possible route for their integrations with electronic and magnetic devices for their advanced applications. Here, we perform element-specific investigations of an emergent class of quasi-2D all-inorganic perovskites Cs2CuCl4–xBrx with (0 ≤ x ≤ 4) using a combination of synchrotron-radiation photoelectron techniques. Surface- and element-sensitive X-ray absorption spectroscopy spectra of Cu L2,3 edges indicate strong electronic transition that is largely influenced by their halogen content at room temperature. This implies that site-selective occupation largely dominates the electronic transition across the unoccupied states of these series since chlorine atoms possess a stronger electronegative character than bromine atoms. Moreover, the implication of halogen site is reflected in the valence band of Cl-rich copper perovskite in which the valence band edge i...

Heterointerfaces have led to the discovery of novel electronic and magnetic states because of their strongly entangled electronic degrees of freedom. Single-phase chromium compounds always exhibit antiferromagnetism following the prediction of Goodenough-Kanamori rules. So far, exchange coupling between chromium ions via hetero-anions has not been explored and the associated quantum states is unknown. Here we report the successful epitaxial synthesis and characterizations of chromium oxide (Cr2O3)-chromium nitride (CrN) superlattices. Room-temperature ferromagnetic spin ordering is achieved at the interfaces between these two antiferromagnets, and the magnitude of the effect decays with increasing layer thickness. First-principles calculations indicate that robust ferromagnetic spin interaction between Cr3+ ions via anion-hybridizations across the interface yields the lowest total energy. This work opens the door to fundamental understanding of the unexpected and exceptional properties of oxide-nitride interfaces and provides access to hidden phases at low-dimensional quantum heterostructures., 21 pages, 4 figures

The effects of atomic-scale disorder and charge (de)localization hold significant importance, and they provide essential insights to unravel the role that strong and weak correlations play in condensed matter systems. In the case of perovskite oxide heterostructures, while disorders introduced via various external stimuli have strong influences over the (de)localization of interfacial two-dimensional (2D) electrons, these factors alone could not fully account for the system's charge dynamics where interfacial hybridization holds very strong influence. Here, we determine that the displaced 2D free electrons have been localized in the specific hybridized states of the LaAlO3/SrTiO3 interface. This experimental study combines both transport measurements and temperature-dependent x-ray absorption spectroscopy and suggests that the localization of 2D electrons can be induced via temperature reduction or ionic liquid gating. Furthermore, this localization effect is found to be applicable to both amorphous and crystalline interfacial systems. In particular, we demonstrate that interfacial hybridization plays a pivotal role in regulating the 2D electron localization effects. Our study resolves the location where the 2D electrons are localized not only does it highlight the importance of interfacial hybridization but it also opens a new avenue for device fabrication in amorphous film systems where charge localization can be done at much great ease as compared to epitaxial crystalline heterostructures.

Intensive effort to tailor photophysics of lead-free perovskites is appealing in recent years. However, their combined electronic and optical property elucidations remain elusive. Here, we report spectroscopic observations of the coexistence Zhang-Rice singlet state and exotic electronic transitions in two-dimensional copper-based perovskites. Herein, several perovskites with different alkylammonium spacers are investigated to unravel their correlated electronic systems and optical responses. Namely, methylammonium, ethylammonium, phenylmethylammonium and phenethylammonium. Using temperature dependent high-resolution X-ray absorption spectroscopy, we observe distinct electronic features highlighting the impact of short spacer chains compared to long-conjugated ligands, demonstrating a pronounced 3d9 and 3d9L signature linewidth variation. Corroborated by density functional theory calculations, the transient dynamics evolution of copper-based hybrid perovskites is influenced by the strong interplay of electron-phonon interactions and geometric constrictions. This finding sheds light on tuning the electronic and optical properties of hybrid perovskites towards efficient photoactive-based devices. Hybrid organic-inorganic perovskites are known to display unique optical properties. Here, electronic transitions in 2D copper-based hybrid perovskites are studied experimentally and theoretically, revealing how ligand size can be used to tune electronic and optical behavior.

Nickel-based complex oxides have served as a playground for decades in the quest for a copper-oxide analog of the high-temperature (high-Tc) superconductivity. They may provide key points towards understanding the mechanism and an alternative route for high-Tc superconductors. The recent discovery of superconductivity in the infinite-layer nickelate thin films has fulfilled this pursuit. Thus far, however, material synthesis remains challenging. The demonstration of perfect diamagnetism is still missing, and understanding of the role of the interface and bulk to the superconducting properties is still lacking. Here, we synthesized high-quality Nd0.8Sr0.2NiO2 thin films with different thicknesses and investigated the interface and strain effects on the electrical, magnetic and optical properties. Perfect diamagnetism is demonstrated, confirming the occurrence of superconductivity in the thin films. Unlike the thick films in which the normal-state Hall coefficient (RH) changes signs as the temperature decreases, the RH of films thinner than 6.1 nm remains negative, suggesting a thickness-driven band structure modification. Moreover, X-ray absorption spectroscopy reveals the Ni-O hybridization nature in doped infinite-layer nickelates, and the hybridization is enhanced as the thickness decreases. Consistent with band structure calculations on the nickelate/SrTiO3 heterostructure, the interface and strain effect induce a dominating electron-like band in the ultrathin film, thus causing the sign change of the RH.

Impurity doping is a viable route toward achieving desired subgap optical response in semiconductors. In strongly excitonic two-dimensional (2D) semiconductors such as transition metal dichalcogenides (TMDs), impurities are expected to result in bound-exciton emission. However, doped TMDs often exhibit a broad Stokes-shifted emission without characteristic features, hampering strategic materials engineering. Here we report observation of a well-defined impurity-induced emission in monolayer WS

Well-ordered spin arrays are highly desirable for next-generation molecule-based magnetic devices, and yet its synthetic method remains a challenging task. Herein, we demonstrate the realization of two-dimensional supramolecular spin arrays on surfaces via halogen-bonding molecular self-assembly. A bromine-terminal perchlorotriphenymethyl radical with net carbon spin was synthesized and deposited on Au(111) to achieve two-dimensional supramolecular spin arrays. By taking advantage of the diversity of halogen bonds, five supramolecular spin arrays are presented with ultrahigh spin densities (up to the value of 3 × 1013 spins at the size of a flash drive), as probed by low-temperature scanning tunneling microscopy at the single-molecule level. First principle calculations verify that the formation of three distinct types of halogen bonds can be used to tailor supramolecular phases via molecular coverage and annealing temperature. Our work demonstrates supramolecular self-assembly as a promising method to engineering 2D spin arrays for potential application in magnetic devices.

Well-ordered spin arrays are highly desirable for next-generation molecule-based magnetic devices, and yet its synthetic method remains a challenging task. Herein, we demonstrate the realization of two-dimensional supramolecular spin arrays on surfaces via halogen-bonding molecular self-assembly. A bromine-terminal perchlorotriphenymethyl radical with net carbon spin was synthesized and deposited on Au(111) to achieve two-dimensional supramolecular spin arrays. By taking advantage of the diversity of halogen bonds, five supramolecular spin arrays are presented with ultrahigh spin densities (up to the value of 3 × 1013 spins at the size of a flash drive), as probed by low-temperature scanning tunneling microscopy at the single-molecule level. First principle calculations verify that the formation of three distinct types of halogen bonds can be used to tailor supramolecular phases via molecular coverage and annealing temperature. Our work demonstrates supramolecular self-assembly as a promising method to engineering 2D spin arrays for potential application in magnetic devices.

The demand for biodegradable and renewable UV-shielding materials is ever increasing due to the rising concern for the environment. In this paper, biobased lignin was functionalized by polyhedral oligomeric silsesquioxane (POSS) with an epoxy substituent. Then the POSS decorated lignin (lignin-POSS) was mixed with polylactide (PLA) to act as UV-shielding filler by melt compounding. The SEM observation revealed that the presence of POSS contributed to improving the homogeneous dispersion of lignin-POSS in the PLA matrix with good compatibility when the content of lignin-POSS was lower than 5 wt%. The synergistic effects of lignin and POSS endowed PLA composite films with a good balance of UV-shielding ability and transparency in the visible light region. With the addition of 5 wt% lignin-POSS, the PLA composite film absorbed almost all UV irradiation across the entire UV spectrum. In addition, the presence of lignin-POSS could serve as a nucleating agent to increase the degree of crystallinity of PLA. The dynamical rheological tests revealed that the lignin-POSSS reduced the complex viscosity and storage modulus of PLA composites, improving the flowability of PLA composites. This work presents a viable pathway to prepare biodegradable and renewable UV-shielding materials for potential packaging applications.

Plasmons, collective excitations of charge density, have attracted much interest in fundamental science and applications. While plasmons have been observed in metal-like phase of high-Tc supercondu...

Epitaxial strain can cause both lattice distortion and oxygen nonstoichiometry, effects that are strongly coupled at heterojunctions of complex nickelate oxides. Here we decouple these structural a...

We report the observation of superconductivity in infinite-layer Ca-doped LaNiO$_2$ (La$_{1-x}$Ca$_x$NiO$_2$) thin films and construct their phase diagram. Unlike the metal-insulator transition in Nd- and Pr-based nickelates, the undoped and underdoped La1-xCaxNiO2 thin films are entirely insulating from 300 K down to 2 K. A superconducting dome is observed at 0.15, Comment: 26 pages, 3 main figures, 6 supplementary figures

The titanomagnetites (Fe

Recent discovery of superconductivity in Nd0.8Sr0.2NiO2 motivates the synthesis of other nickelates for providing insights into the origin of high-temperature superconductivity. However, the synthesis of stoichiometric R1−xSrxNiO3 thin films over a range of x has proven challenging. Moreover, little is known about the structures and properties of the end member SrNiO3. Here, we show that spontaneous phase segregation occurs while depositing SrNiO3 thin films on perovskite oxide substrates by molecular beam epitaxy. Two coexisting oxygen-deficient Ruddlesden-Popper phases, Sr2NiO3 and SrNi2O3, are formed to balance the stoichiometry and stabilize the energetically preferred Ni2+ cation. Our study sheds light on an unusual oxide thin-film nucleation process driven by the instability in perovskite structured SrNiO3 and the tendency of transition metal cations to form their most stable valence (i.e., Ni2+ in this case). The resulting metastable reduced Ruddlesden-Popper structures offer a testbed for further studying emerging phenomena in nickel-based oxides.

An atomically dispersed structure is attractive for electrochemically converting carbon dioxide (CO

The realization of lead-free all-inorganic perovskites in emergent materials requires an in-depth understanding of strongly correlated systems toward optoelectronics or spintronics applications. Herein, we report the electronic and optical variation of the -oriented layered double perovskites (LDP) family with the formula of Cs4MIIBi2Br12 thin films (where MII: Cu, Mn, Pb, or Sr). The element and shell-specific orbital polarization based on soft X-ray linear dichroism spectroscopy probes the Cs M4,5- and Mn L2,3- edges of Cs4MnBi2Br12 thin films as a function of temperature. A strong reversal orbital polarization at the respective edges at 150 K indicates a thermally induced orbital-selective rearrangement at low temperature. In addition, the valence band analysis indicates different orbital admixtures of Br 4p and MII d states, corroborated by the density functional theory calculations. In terms of the transient charge dynamics, we observe the photoluminescence peak maxima position trend line is shifted toward a longer wavelength. In addition, the longest average lifetime is recorded for Cs4CuBi2Br12 at 27.40 ± 1 μs. As the LDP structural integrity is lead-free, therefore, these all-inorganic perovskites hold promising potentials as sustainable and green materials for photophysics applications. Ministry of Education (MOE) The authors acknowledge research grants from Ministry of Education, Singapore with numbers MOE Tier 3 (MOE2014-T3-1-004) and MOE Tier 2 (MOE2018-T2-1-088, MOE2016-T2-1-052, and MOE2019-T2-1-163) and MOE2019-T1-002-063. A. acknowledges funding support from NRF-NSFC grant R-144-000-405-281. M.H.M. acknowledges a research grant no. 139/IT1.B07.1/TA.00/2021 from Institut Teknologi Bandung under the ‘Riset ITB 2021’ scheme.

Epitaxial Fe

Two-dimensional (2D) alloys represent a versatile platform that extends the properties of atomically thin transition-metal dichalcogenides. Here, using molecular beam epitaxy, we investigate the growth of 2D vanadium-molybdenum diselenide alloys, VxMo1-xSe2, on highly oriented pyrolytic graphite and unveil their structural, chemical, and electronic integrities via measurements by scanning tunneling microscopy/spectroscopy, synchrotron X-ray photoemission, and X-ray absorption spectroscopy (XAS). Essentially, we found a critical value of x = similar to 0.44, below which phase separation occurs and above which a homogeneous metallic phase is favored. Another observation is an effective increase in the density of mirror twin boundaries of constituting MoSe2 in the low V concentration regime (x

Dynamic phase segregation, driven by the instability of Ni2+, occurs during SrNiO3 heteroepitaxy growth., Recent discovery of superconductivity in Nd0.8Sr0.2NiO2 motivates the synthesis of other nickelates for providing insights into the origin of high-temperature superconductivity. However, the synthesis of stoichiometric R1−xSrxNiO3 thin films over a range of x has proven challenging. Moreover, little is known about the structures and properties of the end member SrNiO3. Here, we show that spontaneous phase segregation occurs while depositing SrNiO3 thin films on perovskite oxide substrates by molecular beam epitaxy. Two coexisting oxygen-deficient Ruddlesden-Popper phases, Sr2NiO3 and SrNi2O3, are formed to balance the stoichiometry and stabilize the energetically preferred Ni2+ cation. Our study sheds light on an unusual oxide thin-film nucleation process driven by the instability in perovskite structured SrNiO3 and the tendency of transition metal cations to form their most stable valence (i.e., Ni2+ in this case). The resulting metastable reduced Ruddlesden-Popper structures offer a testbed for further studying emerging phenomena in nickel-based oxides.

The quasimetallic 1T′ phase 2D transition‐metal dichalcogenides (TMDs) consist of 1D zigzag metal chains stacked periodically along a single axis. This gives rise to its prominent physical properties which promises the onset of novel physical phenomena and applications. Here, the in‐plane electronic correlations are explored, and new mid‐infrared plasmon excitations in 1T′ phase monolayer WSe2 and MoS2 are observed using optical spectroscopies. Based on an extensive first‐principles study which analyzes the charge dynamics across multiple axes of the atomic‐layered systems, the collective charge excitations are found to disperse only along the direction perpendicular to the chains. Further analysis reveals that the interchain long‐range coupling is responsible for the coherent 1D charge dynamics and the spin–orbit coupling affects the plasmon frequency. Detailed investigation of these charge collective modes in 2D‐chained systems offers opportunities for novel device applications and has implications for the underlying mechanism that governs superconductivity in 2D TMD systems., New 1D mid‐infrared anisotropic plasmons are observed in the quasimetallic phase of WSe2 and MoS2 monolayers. In‐depth analysis reveals that the long‐range inter‐chain coupling is responsible for this 1D charge dynamics, and the plasmon energy is dictated by the effects of spin–orbit coupling. This study establishes an inextricable link between the 1D‐chain structure and charge dynamics in quasimetallic phase 2D transition‐metal dichalcogenides.

Enhancing catalytic activity by decorating noble metals in catalysts provides an opportunity for promoting the electrocatalytic hydrogen evolution reaction (HER) application. However, there are few systematic studies on regulating the structures of noble metals in catalytic materials and investigating their influence on HER. Herein, Pt catalysts with different structures including single atoms (SAs), clusters, and nanoparticles well-controllably anchored on VS