Unlocking Giant Third-Order Optical Nonlinearity in (MA)2CuX4 through Introducing Jahn-Teller Distortion.

Nonlinear absorption coefficient and modulation depth stand as pivotal properties of nonlinear optical (NLO) materials, while the existing NLO materials exhibit limitations such as low nonlinear absorption coefficients and/or small modulation depths, thereby severely impeding their practical application. Here we unveil that introducing Jahn-Teller distortion in a Mott-Hubbard system, (MA)2CuX4 (MA = methylammonium; X = Cl, Br) affords the simultaneous attainment of a giant nonlinear absorption coefficient and substantial modulation depth. The optimized compound, (MA)2CuCl4, demonstrates a nonlinear absorption coefficient of (1.5 ± 0.08) × 105 cm GW-1, a modulation depth of 60%, and a relatively low optical limiting threshold of 1.22 × 10-5 J cm-2. These outstanding attributes surpass those of most reported NLO materials. Our investigation reveals that a more pronounced distortion of the [CuX6]4- octahedron emerges as a crucial factor in augmenting optical nonlinearity. Mechanism study involving structural and spectral characterization along with theoretical calculations indicates a correlation between the compelling performance and the Mott-Hubbard band structure of the materials, coupled with the Jahn-Teller distortion-induced d-d transition. This study not only introduces a promising category of high-performance NLO materials but also provides novel insights into enhancing the performance of such materials.

Low-temperature thermocatalytic removal of formaldehyde in air using copper manganite spinels.

The removal of formaldehyde (FA) is vital for indoor air quality management in light of its carcinogenic propensity and adverse environmental impact. A series of copper manganite spinel structures (e.g., CuMn2O4) are prepared using the sol-gel combustion method and treated with reduction or oxidation pretreatment at 300 °C condition. Accordingly, CuMn2O4-O ("O" suffix for oxidation pre-treatment in air) is identified as the best performer to achieve 100% conversion (XFA) of FA (50 ppm) at 90 °C; its performance, if assessed in terms of reaction kinetic rate (r) at XFA = 10%, is 5.02E-03 mmol g-1 h-1. The FA removal performance increases systematically with decreases in flow rate, FA concentration, and relative humidity (RH) or with increases in bed mass. The reaction pathways and intermediates of FA catalytic oxidation on CuMn2O4-A are studied with density functional theory simulations, temperature-programmed characterization experiments, and in-situ diffuse reflectance infrared Fourier transform spectroscopy. The synergistic combination of large quantities of adsorbed oxygen (OA) species and oxidized metal species (e.g., Cu2+) contribute to the enhanced catalytic performance of CuMn2O4-O to oxidize FA into CO2 with the reaction intermediates of H2CO2 (DOM), HCOO-, and CO. The present study is expected to provide valuable insights into the thermocatalytic oxidation of FA over spinel CuMn2O4 materials and their catalytic performances in relation to the key process variables.

Titanium dioxide-supported mercury photocatalysts for oxidative removal of hydrogen sulfide from the air using a portable air purification unit.

Photocatalytic removal of gaseous hydrogen sulfide (H2S) has been studied through the control of key process variables using a prototype air purifier (AP) fabricated with titanium dioxide (TiO2)-supported mercury. The performance of Hg/TiO2 systems, prepared with different Hg mass proportions over TiO2 (such as 0.1%, 1%, 2%, and 5%), is measured against 5 ppm H2S at 160 L min-1 under UV irradiation. Accordingly, their removal efficiency (RE) values after 360 s are 40.3%, 74.8%, 99.3%, and 99.9%, respectively (relative to 33.5% of AP (TiO2)). An AP with a 2% Hg/TiO2 unit achieves a clean air delivery rate of 32 L min-1 with kinetic reaction rate (r (at 10% RE)) of 0.774 mmol h-1 g-1, quantum yield of 2.19E-02 molecules photon-1, and space-time yield of 1.46E-04 molecules photon-1 mg-1. The superior photocatalytic performance of Hg/TiO2 is supported by superoxide anion and hydroxyl radicals formed in dry air and humid nitrogen (N2) environments, respectively. A density functional theory simulation suggests that the presence of oxygen vacancies should promote the disparities in the electronic structure to subsequently affect the reaction pathways and energetics. The presence of moisture enhances the robust formation of a mercury-OH bond to favorably yield ß-mercury sulfide from H2S.

The practical utility of ternary nickel-cobalt-manganese oxide-supported platinum catalysts for room-temperature oxidative removal of formaldehyde from the air.

Formaldehyde (FA), a carcinogenic oxygenated volatile organic compound, is present ubiquitously in indoor air. As such, it is generally regarded as a critical target for air quality management. The oxidative removal of FA under dark and room-temperature (RT) conditions is of practical significance. A series of ternary nickel-cobalt-manganese oxide-supported platinum catalysts (Pt/NiCoMnO4) have been synthesized for FA oxidative removal at RT in the dark. Their RT conversion values for 50 ppm FA (XFA) at 5,964 h-1 gas hourly space velocity (GHSV) decrease in the following order: 1 wt% Pt/NiCoMnO4 (100 %) > 0.5 wt% Pt/NiCoMnO4 (25 %) > 0.05 wt% Pt/NiCoMnO4 (14 %) > NiCoMnO4 (6 %). The catalytic performance of 1 wt% Pt/NiCoMnO4 has been examined further under the control of various process variables (e.g., catalyst mass, flow rate, relative humidity, FA concentration, time on stream, and molecular oxygen content). The catalytic oxidation of FA at low temperatures (e.g., RT and 60 °C) is accounted for by Langmuir-Hinshelwood mechanism (single-site competitive-adsorption), while Mars van Krevelen kinetics is prevalent at higher temperatures. In situ diffuse-reflectance infrared Fourier-transform spectroscopy reveals that FA oxidation proceeds through a series of reaction intermediates such as DOM, HCOO-, and CO32-. Based on the density functional theory simulations, the unique electronic structures of the nearest surface atoms (platinum and nickel) are suggested to be responsible for the superior catalytic activity of Pt/NiCoMnO4.

Thermocatalytic oxidation of a binary mixture of formaldehyde and toluene at ambient levels by a titanium dioxide supported platinum catalyst.

The thermocatalytic oxidative potential of various supported noble metal catalysts (SNMCs) is well-known for hazardous volatile organic compounds (VOCs), e.g., formaldehyde (FA) and toluene. However, little is known about SNMC performance against ambient VOC pollution with low concentration (subppm levels) relative to industrial effuluents with high concentrations (several hundred ppm). Here, the thermocatalytic oxidation performance of a titanium dioxide (TiO2)-supported platinum catalyst (Pt/TiO2) has been evaluated for a low-concentration binary mixture of FA and toluene at low temperatures and in the dark. A sample of TiO2 containing 1 wt% Pt with thermal reduction pre-treatment under hydrogen achieved 100 % conversion of FA (500 ppb) and toluene (100 ppb) at 130 °C and a gas hourly velocity of 59,701 h-1. Its catalytic activity was lowered by either a decrease in catalyst mass or an increase in VOC concentration, relative humidity, or flow rate. In situ diffuse reflectance infrared Fourier transform spectroscopy, density functional theory simulations, and molecular oxygen (O2) temperature-programmed desorption experiments were used to identify possible VOC oxidation pathways, reaction mechanisms, and associated surface phenomena. The present work is expected to offer insights into the utility of metal oxide-supported Pt catalysts for the low-temperature oxidative removal of gaseous VOCs in the dark, primarily for indoor air quality management.

Isolated Spin-7/2 Species of Gadolinium (III) Chelate Complexes on the Surface of 5-nm Diamond Particles.

The magnetic characteristics of a system of triply charged gadolinium ions Gd3+ chelated with carboxyls on the surface of detonation nanodiamond (DND) particles have been studied. Gd3+ ions demonstrate almost perfect spin (S = 7/2) paramagnetism with negligible antiferromagnetic interaction between spins (Weiss temperature about -0.35 K) for a wide range of concentrations up to ~18 ions per 5 nm particle. The study of the concentration dependence of the electron paramagnetic resonance signal for DND intrinsic defects with spin ½ (g = 2.0027) shows that Gd3+ ions are located on average at a distance of no more than 1.4 nm from shallow subsurface defects with spin 1/2. At the same time, they are located (according to density functional theory calculations) at a distance of about or at least 0.28 nm from the particle surface. Magnetic studies also confirm the isolated nature of the gadolinium chelate complexes on the surface of DND particles. DND particles turn out to be an optimal carrier for high-spin 4f- ions (gadolinium) in a highly concentrated isolated state. This property makes DND-Gd particles a candidate for the role of a contrast agent for magnetic resonance imaging.

Cost-effective, high-performance Ni3Sn4 electrocatalysts for methanol oxidation reaction in acidic environments.

Methanol (CH3OH) oxidation offers a promising avenue for transitioning to clean energy, particularly in the field of direct methanol fuel cells (DMFCs). However, the development of efficient and cost-effective catalysts for the methanol oxidation reaction (MOR) remains a critical challenge. Herein, we report the exceptional electrocatalytic activity and stability of Ni3Sn4 toward MOR in acidic media, achieving a performance comparable to that of commercial Pt/C catalysts. Our catalyst design incorporates Earth-abundant Ni and Sn elements, resulting in a material that is 1800 times more cost-effective than Pt/C. Density functional theory (DFT) modeling substantiates our experimental findings, shedding light on the favorable reaction mechanisms and kinetics on the Ni3Sn4 surface. Additionally, the as-synthesized Ni3Sn4 electrocatalyst demonstrates commendable durability, maintaining its electrocatalytic activity even after prolonged exposure to harsh acidic conditions.

An Isothiazolanthrone-Based Self-Assembling Anticancer Color-Changing Dye for Concurrent Imaging and Monitoring of Cell Viability.

We report the photophysical properties, self-assembly and biological evaluation of an isothiazolanthrone-based dye, 7-amino-6H-anthra[9,1-cd]isothiazol-6-one (AAT), which reveals anticancer properties and can be potentially used as dye for monitoring cell viability. The solvent-dependent photophysical studies suggest that the emission of AAT is sensitive to environment polarity due to which interesting changes in the colored emission may be observed owing to the charge transfer (CT) processes. AAT also self-assembles to tree-like branched morphologies and produce, a greenish emission inside the cells when imaged after short interval (15 mins) of incubation while a red fluorescence could be noted after 24 h. Interestingly, AAT also produce differential emission inside mouse normal cells as compared to its cancer cell lines since it possess anticancer activity. The experimental observations were also validated theoretically via computational modeling.

Unveiling the Catalytic Potential of Topological Nodal-Line Semimetal AuSn4 for Hydrogen Evolution and CO2 Reduction.

In recent years, the correlation between the existence of topological electronic states in materials and their catalytic activity has gained increasing attention, due to the exceptional electron conductivity and charge carrier mobility exhibited by quantum materials. However, the physicochemical mechanisms ruling catalysis with quantum materials are not fully understood. Here, we investigate the chemical reactivity, ambient stability, and catalytic activity of the topological nodal-line semimetal AuSn4. Our findings reveal that the surface of AuSn4 is prone to oxidation, resulting in the formation of a nanometric SnO2 skin. This surface oxidation significantly enhances the material's performance as a catalyst for the hydrogen evolution reaction in acidic environments. We demonstrate that the peculiar atomic structure of oxidized AuSn4 enables the migration of hydrogen atoms through the Sn-O layer with a minimal energy barrier of only 0.19 eV. Furthermore, the Volmer step becomes exothermic in the presence of Sn vacancies or tin-oxide skin, as opposed to being hindered in the pristine sample, with energy values of -0.62 and -1.66 eV, respectively, compared to the +0.46 eV energy barrier in the pristine sample. Our model also suggests that oxidized AuSn4 can serve as a catalyst for the hydrogen evolution reaction in alkali media. Additionally, we evaluate the material's suitability for the carbon dioxide reduction reaction, finding that the presence of topologically protected electronic states enhances the migration of hydrogen atoms adsorbed on the catalyst to carbon dioxide.

Hydrogen Production Mechanism in Low-Temperature Methanol Decomposition Catalyzed by Ni3Sn4 Intermetallic Compound: A Combined Operando and Density Functional Theory Investigation.

Hydrogen production from methanol decomposition to syngas (H2 + CO) is a promising alternative route for clean energy transition. One major challenge is related to the quest for stable, cost-effective, and selective catalysts operating below 400 °C. We illustrate an investigation of the surface reactivity of a Ni3Sn4 catalyst working at 250 °C, by combining density functional theory, operando X-ray absorption spectroscopy, and high-resolution transmission electron microscopy. We discovered that the catalytic reaction is driven by surface tin-oxide phases, which protects the underlying Ni atoms from irreversible chemical modifications, increasing the catalyst durability. Moreover, we found that Sn content plays a key role in enhancing the H2 selectivity, with respect to secondary products such as CO2. These findings open new perspectives for the engineering of scalable and low-cost catalysts for hydrogen production.

A comprehensive model of nitrogen-free ordered carbon quantum dots.

We propose and demonstrate a novel range of models to accurately determine the optical properties of nitrogen-free carbon quantum dots (CQDs) with ordered graphene layered structures. We confirm the results of our models against the full range of experimental results for CQDs available from an extensive review of the literature. The models can be equally applied to CQDs with varied sizes and with different oxygen contents in the basal planes of the constituent graphenic sheets. We demonstrate that the experimentally observed blue fluorescent emission of nitrogen-free CQDs can be associated with either small oxidised areas on the periphery of the graphenic sheets, or with sub-nanometre non-functionalised islands of sp2-hybridised carbon with high symmetry confined in the centres of oxidised graphene sheets. Larger and/or less symmetric non-functionalised regions in the centre of functionalised graphene sheet are found to be sources of green and even red fluorescent emission from nitrogen-free CQDs. We also demonstrate an approach to simplify the modelling of the discussed sp2-islands by substitution with equivalent strained polycyclic aromatic hydrocarbons. Additionally, we show that the bandgaps (and photoluminescence) of CQDs are not dependent on either out-of-plane corrugation of the graphene sheet or the spacing between sp2-islands. Advantageously, our proposed models show that there is no need to involve light-emitting polycyclic aromatic molecules (nanographenes) with arbitrary structures grafted to the particle periphery to explain the plethora of optical phenomena observed for CQDs across the full range of experimental works.

NiSe and CoSe Topological Nodal-Line Semimetals: A Sustainable Platform for Efficient Thermoplasmonics and Solar-Driven Photothermal Membrane Distillation.

The control of heat at the nanoscale via the excitation of localized surface plasmons in nanoparticles (NPs) irradiated with light holds great potential in several fields (cancer therapy, catalysis, desalination). To date, most thermoplasmonic applications are based on Ag and Au NPs, whose cost of raw materials inevitably limits the scalability for industrial applications requiring large amounts of photothermal NPs, as in the case of desalination plants. On the other hand, alternative nanomaterials proposed so far exhibit severe restrictions associated with the insufficient photothermal efficacy in the visible, the poor chemical stability, and the challenging scalability. Here, it is demonstrated the outstanding potential of NiSe and CoSe topological nodal-line semimetals for thermoplasmonics. The anisotropic dielectric properties of NiSe and CoSe activate additional plasmonic resonances. Specifically, NiSe and CoSe NPs support multiple localized surface plasmons in the optical range, resulting in a broadband matching with sunlight radiation spectrum. Finally, it is validated the proposed NiSe and CoSe-based thermoplasmonic platform by implementing solar-driven membrane distillation by adopting NiSe and CoSe nanofillers embedded in a polymeric membrane for seawater desalination. Remarkably, replacing Ag with NiSe and CoSe for solar membrane distillation increases the transmembrane flux by 330% and 690%, respectively. Correspondingly, costs of raw materials are also reduced by 24 and 11 times, respectively. The results pave the way for the advent of NiSe and CoSe for efficient and sustainable thermoplasmonics and related applications exploiting sunlight within the paradigm of the circular blue economy.

On the atomic structure of two-dimensional materials with Janus structures.

The discrepancy between the bright theoretical projections for two-dimensional (2D) Janus structures and the lack of experimental realisation of these structures motivated us to study the effect of structural disorder on the stability of MoSSe, SnSSe, PtSSe, In2SSe and GaInSe2. The calculation results demonstrate that the difference between metal-sulfur and metal-selenium bonds makes Janus structures frustrated and less energetically favourable than less ordered allotropes of the same compounds. This result explains the difficulties encountered in the experimental fabrication of these materials. In the bulk, there is an additional contribution to the total energy from dipole-dipole interactions between layers with a Janus structure that can overcome the energetic cost of structural frustration in layers for compounds with sufficiently large dipole moments. However, the entropic contribution to the free energy decreases the favourability of the ordered Janus structure. The calculation results are used to make recommendations to enable the discovery and synthesis of 2D materials with Janus structures.

Low-temperature oxidative removal of gaseous formaldehyde by an eggshell waste supported silver-manganese dioxide bimetallic catalyst with ultralow noble metal content.

Under dark/low temperature (DLT) conditions, the oxidative removal of gaseous formaldehyde (FA) was studied using eggshell waste supported silver (Ag)-manganese dioxide (MnO2) bimetallic catalysts. To assess the synergistic effects between the two different metals, 0.03%-Ag-(0.5-5%)-MnO2/Eggshell catalysts were prepared and employed for DLT-oxidation of FA. The steady-state FA oxidation reaction rate (mmol g-1 h-1), when measured using 100 ppm FA at 80 °C (gas hourly space velocity (GHSV) of 5308 h-1), varied as follows: Ag-1.5%-MnO2/Eggshell-R (9.4) > Ag-3%-MnO2/Eggshell-R (8.1) > Ag-1.5%-MnO2/Eggshell (7.5) > Ag-5%-MnO2/Eggshell-R (7.2) > Ag-1.5%-MnO2/CaCO3-R (6.8) > MnO2-R (6) > Ag-0.5%-MnO2/Eggshell-R (3.2) > Ag/Eggshell-R (2.6). (Here, 'R' denotes hydrogen-based thermochemical reduction pretreatment.) The temperature required for 90% FA conversion (T90) at the same GHSV exhibited a contrary ordering: Ag/Eggshell-R (175 °C) > Ag-0.5%-MnO2/Eggshell-R (123 °C) > Ag-5%-MnO2/Eggshell-R (113 °C) > MnO2-R (99 °C) > Ag-1.5%-MnO2/Eggshell (96 °C) > Ag-3%-MnO2/Eggshell-R (93 °C) > Ag-1.5%-MnO2/Eggshell-R (77 °C). The eggshell catalyst outperformed the ones made of commercial calcium carbonate due to the presence of defects in the former. The MnO2 co-catalyst enhances the catalytic activities through the capture and activation of atmospheric oxygen (O2) with rapid catalytic regeneration. Also, MnO2 favorably captures the hydrogen of the adsorbed FA molecules to make the oxidation pathway thermodynamically more favorable.

A new aggregation induced emission enhancement (AIEE) dye which self-assembles to panchromatic fluorescent flowers and has application in sensing dichromate ions.

We report for the very first time the crystal structure and self-assembly of a new aggregation-induced emission enhancement (AIEE) dye 4-(5-methoxythiazolo[4,5-b]pyridin-2-yl)-N,N-dimethylaniline (TPA) and its application in sensing dichromate ions. TPA reveals cyan blue emission under UV and visible light. The self-assembly properties of TPA were studied extensively by scanning electron microscopy (SEM) which revealed the formation of beautiful flower-like morphologies. These structures revealed both green and red fluorescence under FITC and rhodamine filters respectively when observed through fluorescence microscopy connoting the panchromatic emission properties of TPA from blue to red. The interactions which cause self-assembled structure formation in TPA were also validated theoretically using density functional theory (DFT) calculations. Crystal and molecular structure analysis of TPA was carried out via single-crystal X-ray diffraction to visualize the intermolecular interactions occurring in the solid-state and to study the structure-photophysical property relationship in the aggregated state. The photophysical properties of TPA were also studied extensively by UV-visible and fluorescence spectroscopy and its quantum yield and fluorescence lifetime were calculated by time-correlated single-photon counting (TCSPC). Interestingly, TPA could efficiently sense dichromate (Cr2O72-) ions in an acidic medium and an interesting morphological transition from a fluorescent flower to non-fluorescent disassembled structures could also be observed. The limit of detection of TPA for Cr2O72- ions was found to be as low as 5.5 nM, suggesting its exceptional sensitivity. More importantly, TPA could selectively sense Cr2O72- ions in real water samples even in the presence of other metal ions routinely present in polluted water, hence making it practically useful for water quality monitoring.

Efficient Hydrogen Evolution Reaction with Bulk and Nanostructured Mitrofanovite Pt3Te4.

Here, we discuss the key features of electrocatalysis with mitrofanovite (Pt3Te4), a recently discovered mineral with superb performances in hydrogen evolution reaction. Mitrofanovite is a layered topological metal with spin-polarized topological surface states with potential applications for spintronics. However, mitrofanovite is also an exceptional platform for electrocatalysis, with costs of the electrodes suppressed by 47% owing to the partial replacement of Pt with Te. Remarkably, the Tafel slope in nanostructured mitrofanovite is just 33 mV/dec, while reduced mitrofanovite has the same Tafel slope (36 mV/dec) as state-of-the-art electrodes of pure Pt. Mitrofanovite also affords surface stability and robustness to CO poisoning. Accordingly, these findings pave the way for the advent of mitrofanovite for large-scale hydrogen production.

Tin Diselenide (SnSe2) Van der Waals Semiconductor: Surface Chemical Reactivity, Ambient Stability, Chemical and Optical Sensors.

Tin diselenide (SnSe2) is a layered semiconductor with broad application capabilities in the fields of energy storage, photocatalysis, and photodetection. Here, we correlate the physicochemical properties of this van der Waals semiconductor to sensing applications for detecting chemical species (chemosensors) and millimeter waves (terahertz photodetectors) by combining experiments of high-resolution electron energy loss spectroscopy and X-ray photoelectron spectroscopy with density functional theory. The response of the pristine, defective, and oxidized SnSe2 surface towards H2, H2O, H2S, NH3, and NO2 analytes was investigated. Furthermore, the effects of the thickness were assessed for monolayer, bilayer, and bulk samples of SnSe2. The formation of a sub-nanometric SnO2 skin over the SnSe2 surface (self-assembled SnO2/SnSe2 heterostructure) corresponds to a strong adsorption of all analytes. The formation of non-covalent bonds between SnO2 and analytes corresponds to an increase of the magnitude of the transferred charge. The theoretical model nicely fits experimental data on gas response to analytes, validating the SnO2/SnSe2 heterostructure as a suitable playground for sensing of noxious gases, with sensitivities of 0.43, 2.13, 0.11, 1.06 [ppm]-1 for H2, H2S, NH3, and NO2, respectively. The corresponding limit of detection is 5 ppm, 10 ppb, 250 ppb, and 400 ppb for H2, H2S, NH3, and NO2, respectively. Furthermore, SnSe2-based sensors are also suitable for fast large-area imaging applications at room temperature for millimeter waves in the THz range.

Switching the Nonlinear Optical Absorption of Titanium Carbide MXene by Modulation of the Surface Terminations.

Surface terminations of two-dimensional materials should have a strong influence on the nonlinear optical (NLO) properties, but the relationship between surface terminations and NLO properties has not yet been reported. In this work, switching the NLO properties of MXenes (Ti3C2Tx) via "surface terminations modulation" is explored. The surface terminations of Ti3C2Tx are modulated by electrochemical treatment, resulting in different states (viz., Ti3C2Tx(pristine), Ti3C2Tx(═O rich), and Ti3C2Tx(-OH rich)). The sign and magnitude of the effective NLO absorption coefficient (ßeff) change with the surface terminations. Ti3C2Tx(═O rich) shows a relatively large saturable absorption (SA) with laser excitation at 515 nm (ßeff = -1020 ± 136.2 cm GW-1), while reverse saturable absorption (RSA) is found in Ti3C2Tx(pristine) and Ti3C2Tx(-OH rich). The RSA of Ti3C2Tx(pristine) and Ti3C2Tx(-OH rich) is attributed to excited-state absorption, while the SA of Ti3C2Tx(═O rich) is associated with Pauli blocking. With laser excitation at 800 nm, the ßeff of Ti3C2Tx(-OH rich) is 113 ± 3.2 cm GW-1, 1.68 times that of Ti3C2Tx(pristine); the RSA is caused by photon-induced absorption. Our results reveal a correlation between surface terminations and NLO properties, highlighting the potential of MXenes in photoelectronics.

Mitrofanovite Pt3Te4: A Topological Metal with Termination-Dependent Surface Band Structure and Strong Spin Polarization.

Due to their peculiar quasiparticle excitations, topological metals have high potential for applications in the fields of spintronics, catalysis, and superconductivity. Here, by combining spin- and angle-resolved photoemission spectroscopy, scanning tunneling microscopy/spectroscopy, and density functional theory, we discover surface-termination-dependent topological electronic states in the recently discovered mitrofanovite Pt3Te4. Mitrofanovite crystal is formed by alternating, van der Waals bound layers of Pt2Te2 and PtTe2. Our results demonstrate that mitrofanovite is a topological metal with termination-dependent (i) electronic band structure and (ii) spin texture. Despite their distinct electronic character, both surface terminations are characterized by electronic states exhibiting strong spin polarization with a node at the Γ point and sign reversal across the Γ point, indicating their topological nature and the possibility of realizing two distinct electronic configurations (both of them with topological features) on the surface of the same material.

Unveiling the Mechanisms Ruling the Efficient Hydrogen Evolution Reaction with Mitrofanovite Pt3Te4.

By means of electrocatalytic tests, surface-science techniques and density functional theory, we unveil the physicochemical mechanisms ruling the electrocatalytic activity of recently discovered mitrofanovite (Pt3Te4) mineral. Mitrofanovite represents a very promising electrocatalyst candidate for energy-related applications, with a reduction of costs by 47% compared to pure Pt and superior robustness to CO poisoning. We show that Pt3Te4 is a weak topological metal with the Z2 invariant, exhibiting electrical conductivity (∼4 × 106 S/m) comparable with pure Pt. In hydrogen evolution reaction (HER), the electrode based on bulk Pt3Te4 shows a very small overpotential of 46 mV at 10 mA cm-2 and a Tafel slope of 36-49 mV dec-1 associated with the Volmer-Heyrovsky mechanism. The outstanding ambient stability of Pt3Te4 also provides durability of the electrode and long-term stability of its efficient catalytic performances.