Near-infrared Rhodols-based fluorescent probe with large Stokes shift for tracking of H2S in food spoilage and living cells.

Hydrogen sulfide (H2S), as a biomarker signaling gas, is not only susceptible to food spoilage, but also plays a key function in many biological processes. In this work, an activated near infrared (NIR) H2S fluorescent probe was designed and synthesized with quinoline-conjugated Rhodols dye as fluorophore skeleton and a dinitrophenyl group as the responsive moiety. Due to the quenching effect of dinitrophenyl group and the closed-loop structure of Rhodols fluorophore, probe itself has a very weak absorption and fluorescence background signal. After the H2S-induced thiolysis reaction, the probe exhibits a remarkable colormetric change and NIR fluorescent enhancement response at 716 nm with large Stokes shift (116 nm), and possesses high sensing selectivity and sensitivity with a low detection limits of 330 nM. The response mechanism is systematically characterized by 1H NMR, MS and DFT calculations. The colorimetric change allows the probe to be used as a test strips to detect H2S in food spoilage, while NIR fluorescent response helps the probe monitor intracellular H2S.

Observation on Microenvironment Changes of Dynamic Catalysts in Acidic CO2 Reduction.

Electrochemical CO2 reduction reaction (CO2RR) in acid can solve alkalinity issues while highly corrosive and reductive acidic electrolytes usually cause catalyst degradation. Inhibiting catalyst degradation is crucial for the stability of acidic CO2RR. Here, we reveal the microenvironment changes of dynamic Bi-based catalysts and develop a pulse chronoamperometry (CA) strategy to improve the stability of acidic CO2RR. In situ fluorescence mappings show that the local pH changes from neutral to acid, and the in situ Raman spectra reveal the dynamic evolution of interfacial water structures in the microenvironment. We propose that the surface charge properties of dynamic catalysts affect the competitive adsorption of K+ and protons, thereby causing the differences in local pH and CO2RR intermediate adsorption. We also develop a pulse CA strategy to reactivate catalysts, and the stability of acidic CO2RR is improved by 2 orders of magnitude for 100 h operation, which is higher than most reports on the stability of acidic CO2RR. This work gives insights on how microenvironment changes affecting the stability of acidic CO2RR, and provides guidance for designing stable catalysts in acidic electrolytes.

Growth of 2D Cr2 O3 -CrN Mosaic Heterostructures with Tunable Room-Temperature Ferromagnetism.

2D magnets have generated much attention due to their potential for spintronic devices. Heterostructures of 2D magnets are interesting platforms for exploring physical phenomena and applications. However, the controlled growth of 2D room-temperature ferromagnetic heterostructures is challenging. Here, one-pot chemical vapor deposition growth of stable 2D Cr2 O3 -CrN mosaic heterostructures (MHs) is reported with a controlled ratio of components that possess robust room-temperature ferromagnetism. The 2D MHs consist of Cr2 O3 flakes with embedded CrN subdomains and the CrN:Cr2 O3 ratio can be tuned from 0% to 100% during growth. By changing the CrN:Cr2 O3 ratio, the ferromagnetism of the MHs (e.g., saturation magnetization, coercive field), which originates from the interfacial coupling between Cr2 O3 and CrN, can be controlled. Importantly, the obtained Cr2 O3 -CrN MHs are stable in air at elevated temperatures and have robust ferromagnetism with Curie temperature >400 K. This work presents a facile method for fabricating 2D MHs with tunable magnetism which will benefit high-temperature spintronics.

Ampere-Level Current Density CO2 Reduction with High C2+ Selectivity on La(OH)3-Modified Cu Catalysts.

The carbon dioxide reduction reaction (CO2RR) driven by electricity can transform CO2 into high-value multi-carbon (C2+) products. Copper (Cu)-based catalysts are efficient but suffer from low C2+ selectivity at high current densities. Here La(OH)3 in Cu catalyst is introduced to modify its electronic structure towards efficient CO2RR to C2+ products at ampere-level current densities. The La(OH)3/Cu catalyst has a remarkable C2+ Faradaic efficiency (FEC2+) of 71.2% which is 2.2 times that of the pure Cu catalyst at a current density of 1,000 mA cm-2 and keeps stable for 8 h. In situ spectroscopy and density functional theory calculations both show that La(OH)3 modifies the electronic structure of Cu. This modification favors *CO adsorption, subsequent hydrogenation, *CO─*COH coupling, and consequently increases C2+ selectivity. This work provides a guidance on facilitating C2+ product formation, and suppressing hydrogen evolution by La(OH)3 modification, enabling efficient CO2RR at ampere-level current densities.

Universal and Energy-Efficient Approach to Synthesize Pt-Rare Earth Metal Alloys for Proton Exchange Membrane Fuel Cell.

Traditional synthesis methods of platinum-rare earth metal (Pt-RE) alloys usually involve harsh conditions and high energy consumption because of the low standard reduction potentials and high oxophilicity of RE metals. In this work, a one-step strategy is developed by rapid Joule thermal-shock (RJTS) to synthesize Pt-RE alloys within tens of seconds. The method can not only realize the regulation of alloy size, but also a universal method for the preparation of a family of Pt-RE alloys (RE = Ce, La, Gd, Sm, Tb, Y). In addition, the energy consumption of the Pt-RE alloy preparation is only 0.052 kW h, which is 2-3 orders of magnitude lower than other reported methods. This method allows individual Pt-RE alloy to be embedded in the carbon substrate, endowing the alloy catalyst excellent durability for oxygen reduction reaction (ORR). The performance of alloy catalyst shows negligible decay after 20k accelerated durability testing (ADT) cycles. This strategy offers a new route to synthesize noble/non-noble metal alloys with diversified applications besides ORR.

A La2O3/MXene composite electrode for supercapacitors with improved capacitance and cycling performance.

Developing efficient electrode materials is a key towards high power electrochemical energy storage devices. Two-dimensional (2D) MXene shows excellent conductivity and electrochemical performance among other materials. However, the restacking of MXene layers may degrade their specific capacity and cycling performance. Considering this challenge, here we have designed a composite made of 2D MXene nanosheets and lanthanum oxide (La2O3) nanoparticles to overcome the limitations. The bifunctionality of La2O3 nanoparticles prevents the restacking of MXene layers and enhances the electrochemical properties of the electrode due to its good Faradic characteristics. The specific capacitance of the La2O3/MXene composite electrode is 366 F/g at 1 A/g, which is 4.5 and 3 times higher than those of the individual La2O3 and MXene. The composite electrode displays a capacitance retention of 96% after 1,000 cycles, which is due to synergistic effects between the two components and indicates the potential of La2O3/MXene composite for supercapacitors.

A corrosion-resistant RuMoNi catalyst for efficient and long-lasting seawater oxidation and anion exchange membrane electrolyzer.

Direct seawater electrolysis is promising for sustainable hydrogen gas (H2) production. However, the chloride ions in seawater lead to side reactions and corrosion, which result in a low efficiency and poor stability of the electrocatalyst and hinder the use of seawater electrolysis technology. Here we report a corrosion-resistant RuMoNi electrocatalyst, in which the in situ-formed molybdate ions on its surface repel chloride ions. The electrocatalyst works stably for over 3000 h at a high current density of 500 mA cm-2 in alkaline seawater electrolytes. Using the RuMoNi catalyst in an anion exchange membrane electrolyzer, we report an energy conversion efficiency of 77.9% and a current density of 1000 mA cm-2 at 1.72 V. The calculated price per gallon of gasoline equivalent (GGE) of the H2 produced is $ 0.85, which is lower than the 2026 technical target of $ 2.0/GGE set by the United Stated Department of Energy, thus, suggesting practicability of the technology.

Two-Dimensional Metal Coordination Polymer Derived Indium Nanosheet for Efficient Carbon Dioxide Reduction to Formate.

Main group indium materials have been known as promising electrocatalysts for two-electron-involved carbon dioxide reduction to produce formate, which is a key energy vector in many industrial reactions. However, the synthesis of two-dimensional (2D) monometallic nonlayered indium remains a great challenge. Here, we present a facile electrochemical reduction strategy to transform 2D indium coordination polymer into elemental indium nanosheets. In a customized flow cell, the reconstructed metallic indium exhibits a high Faradaic efficiency (FE) of 96.3% for formate with a maximum partial current density exceeding 360 mA cm-2 and negligible degradation after 140 h operation in 1 M KOH solution, outperforming the state-of-the-art indium-based electrocatalysts. Moreover, in and ex situ electrochemical analysis and characterizations demonstrate that the enhanced exposure of active sites and mass/charge transport at the CO2 gas-catalyst-electrolyte triple-phase interface and the restrained electrolyte flooding are contributing to producing and stabilizing carbon dioxide radical anion intermediates, thus leading to superior catalytic performance.

Dual interfacial engineering of a Chevrel phase electrode material for stable hydrogen evolution at 2500 mA cm-2.

Constructing stable electrodes which function over long timescales at large current density is essential for the industrial realization and implementation of water electrolysis. However, rapid gas bubble detachment at large current density usually results in peeling-off of electrocatalysts and performance degradation, especially for long term operations. Here we construct a mechanically-stable, all-metal, and highly active CuMo6S8/Cu electrode by in-situ reaction between MoS2 and Cu. The Chevrel phase electrode exhibits strong binding at the electrocatalyst-support interface with weak adhesion at electrocatalyst-bubble interface, in addition to fast hydrogen evolution and charge transfer kinetics. These features facilitate the achievement of large current density of 2500 mA cm-2 at a small overpotential of 334 mV which operate stably at 2500 mA cm-2 for over 100 h. In-situ total internal reflection imaging at micrometer level and mechanical tests disclose the relationships of two interfacial forces and performance of electrocatalysts. This dual interfacial engineering strategy can be extended to construct stable and high-performance electrodes for other gas-involving reactions.

Space-Confined One-Step Growth of 2D MoO2 /MoS2 Vertical Heterostructures for Superior Hydrogen Evolution in Alkaline Electrolytes.

2D material-based heterostructures are constructed by stacking or spicing individual 2D layers to create an interface between them, which have exotic properties. Here, a new strategy for the in situ growth of large numbers of 2D heterostructures on the centimeter-scale substrate is developed. In the method, large numbers of 2D MoS2 , MoO2 , or their heterostructures of MoO2 /MoS2 are controllably grown in the same setup by simply tuning the gap distance between metal precursor and growth substrate, which changes the concentration of metal precursors feed. A lateral force microscope is used first to identify the locations of each material in the heterostructures, which have MoO2 on the top of MoS2 . Noteworthy, the creation of a clean interface between atomic thin MoO2 (metallic) and MoS2 (semiconducting) results in a different electronic structure compared with pure MoO2 and MoS2 . Theoretical calculations show that the charge redistribution at such an interface results in an improved HER performance on the MoO2 /MoS2 heterostructures, showing an overpotential of 60 mV at 10 mA cm-2 and a Tafel slope of 47 mV dec-1 . This work reports a new strategy for the in situ growth of heterostructures on large-scale substrates and provides platforms to exploit their applications.

A 2D material-based transparent hydrogel with engineerable interference colours.

Transparent hydrogels are key materials for many applications, such as contact lens, imperceptible soft robotics and invisible wearable devices. Introducing large and engineerable optical anisotropy offers great prospect for endowing them with extra birefringence-based functions and exploiting their applications in see-through flexible polarization optics. However, existing transparent hydrogels suffer from limitation of low and/or non-fine engineerable birefringence. Here, we invent a transparent magneto-birefringence hydrogel with large and finely engineerable optical anisotropy. The large optical anisotropy factor of the embedded magnetic two-dimensional material gives rise to the large magneto-birefringence of the hydrogel in the transparent condition of ultra-low concentration, which is several orders of magnitude larger than usual transparent magnetic hydrogels. High transparency, large and tunable optical anisotropy cooperatively permit the magnetic patterning of interference colours in the hydrogel. The hydrogel also shows mechanochromic and thermochromic property. Our finding provides an entry point for applying hydrogel in optical anisotropy and colour centred fields, with several proof-of-concept applications been demonstrated.

A Ta-TaS2 monolith catalyst with robust and metallic interface for superior hydrogen evolution.

The use of highly-active and robust catalysts is crucial for producing green hydrogen by water electrolysis as we strive to achieve global carbon neutrality. Noble metals like platinum are currently used catalysts in industry for the hydrogen evolution, but suffer from scarcity, high price and unsatisfied performance and stability at large current density, restrict their large-scale implementations. Here we report the synthesis of a type of monolith catalyst consisting of a metal disulfide (e.g., tantalum sulfides) vertically bonded to a conductive substrate of the same metal tantalum by strong covalent bonds. These features give the monolith catalyst a mechanically-robust and electrically near-zero-resistance interface, leading to an excellent hydrogen evolution performance including rapid charge transfer and excellent durability, together with a low overpotential of 398 mV to achieve a current density of 2,000 mA cm-2 as required by industry. The monolith catalyst has a negligible performance decay after 200 h operation at large current densities. In light of its robust and metallic interface and the various choices of metals giving the same structure, such monolith materials would have broad uses besides catalysis.

High-throughput production of cheap mineral-based two-dimensional electrocatalysts for high-current-density hydrogen evolution.

The high-throughput scalable production of cheap, efficient and durable electrocatalysts that work well at high current densities demanded by industry is a great challenge for the large-scale implementation of electrochemical technologies. Here we report the production of a two-dimensional molybdenum disulfide-based ink-type electrocatalyst by a scalable exfoliation technique followed by a thermal treatment. The catalyst delivers a high current density of 1000 mA cm-2 at an overpotential of 412 mV for the hydrogen evolution. Using the same method, we produce a cheap mineral-based catalyst possessing excellent performance for high-current-density hydrogen evolution. Noteworthy, production rate of this catalyst is one to two orders of magnitude higher than those previously reported, and price of the mineral is five orders of magnitude lower than commercial Pt electrocatalysts. These advantages indicate the huge potentials of this method and of mineral-based cheap and abundant natural resources as catalysts in the electrochemical industry.

Controllable structure reconstruction of nickel-iron compounds toward highly efficient oxygen evolution.

Nickel-iron (Ni-Fe) compounds have received ever-increasing interest because of their high performance for the oxygen evolution reaction (OER). However, the structure and composition of the active phase of Ni-Fe compounds are not yet understood. Rational design of Ni-Fe compounds with proper composition and exposed active sites is highly desirable to further improve their performance. Here we reported the synthesis of different Ni-Fe compounds by incorporating Fe into the Ni(OH)2 lattice with controlled concentrations and obtained several products including Ni-Fe layered double hydroxides (LDHs) with different amounts of Fe and NiFe2O4. In addition, ß-Ni(OH)2 without Fe and α-Fe2O3 without Ni have also been synthesized for comparison. Among these four Ni/Fe based compounds, we found that the two-dimensional (2D) Ni0.8Fe0.2-LDH nanosheets with a hexagonal shape manifest a highest OER activity with a lowest overpotential of 235 mV at 10 mA cm-2, a smallest Tafel slope of 41 mV dec-1 and excellent stability over 24 h. In situ Raman, X-ray absorption spectroscopy and X-ray photoelectron spectroscopy show that the enhanced activity of Ni0.8Fe0.2-LDH is due to the increased oxidation state of Ni from Ni2+ to Ni3+. Our findings demonstrate that the composition of Ni-Fe compounds influences the oxidizing ability of Ni and consequently their catalytic performance. We also reveal a strong correlation between the structure and oxidizing power of the Ni in Ni-Fe compounds and their OER activity, indicating that the well-engineered structure and Ni-site electronics are the primary origins of their OER activity. This work not only provides a promising guideline for the design and synthesis of Ni/Fe based compounds, but also highlights the crucial role of each component in enhancing the activity of these electrocatalysts.

Dual-Additive Assisted Chemical Vapor Deposition for the Growth of Mn-Doped 2D MoS2 with Tunable Electronic Properties.

Doping of bulk silicon and III-V materials has paved the foundation of the current semiconductor industry. Controlled doping of 2D semiconductors, which can also be used to tune their bandgap and type of carrier thus changing their electronic, optical, and catalytic properties, remains challenging. Here the substitutional doping of nonlike element dopant (Mn) at the Mo sites of 2D MoS2 is reported to tune its electronic and catalytic properties. The key for the successful incorporation of Mn into the MoS2 lattice stems from the development of a new growth technology called dual-additive chemical vapor deposition. First, the addition of a MnO2 additive to the MoS2 growth process reshapes the morphology and increases lateral size of Mn-doped MoS2 . Second, a NaCl additive helps in promoting the substitutional doping and increases the concentration of Mn dopant to 1.7 at%. Because Mn has more valance electrons than Mo, its doping into MoS2 shifts the Fermi level toward the conduction band, resulting in improved electrical contact in field effect transistors. Mn doping also increases the hydrogen evolution activity of MoS2 electrocatalysts. This work provides a growth method for doping nonlike elements into 2D MoS2 and potentially many other 2D materials to modify their properties.

Tuning the Hydrogen Evolution Performance of Metallic 2D Tantalum Disulfide by Interfacial Engineering.

Metallic transition metal dichalcogenides, such as tantalum disulfide (TaS2), have recently emerged as promising electrocatalysts for the hydrogen evolution reaction. This work reports an effective strategy to further tune their performance through interfacial engineering, including lattice mismatch and electron injection between electrocatalysts and the underlying substrates. A unique two-zone chemical vapor deposition technique has been developed, and 2D TaS2 has been successfully grown on four different substrates, including glassy carbon, carbon fibers, Mo foil, and Au foil, providing excellent platforms to study catalyst-substrate interactions. Among them, TaS2 on Au foil offers the best performance with lowest overpotential and smallest charge transfer resistance, due to a suitable lattice mismatch and charge injection between TaS2 and Au, as revealed by theoretical calculations and experimental measurements. This work highlights the key roles the substrate plays in the catalysis and demonstrates the validity of interfacial engineering in catalyst design.

Morphology and surface chemistry engineering toward pH-universal catalysts for hydrogen evolution at high current density.

Large-scale implementation of electrochemical hydrogen production requires several fundamental issues to be solved, including understanding the mechanism and developing inexpensive electrocatalysts that work well at high current densities. Here we address these challenges by exploring the roles of morphology and surface chemistry, and develop inexpensive and efficient electrocatalysts for hydrogen evolution. Three model electrocatalysts are flat platinum foil, molybdenum disulfide microspheres, and molybdenum disulfide microspheres modified by molybdenum carbide nanoparticles. The last catalyst is highly active for hydrogen evolution independent of pH, with low overpotentials of 227 mV in acidic medium and 220 mV in alkaline medium at a high current density of 1000 mA cm-2, because of enhanced transfer of mass (reactants and hydrogen bubbles) and fast reaction kinetics due to surface oxygen groups formed on molybdenum carbide during hydrogen evolution. Our work may guide rational design of electrocatalysts that work well at high current densities.

MnO2 Nanofilms on Nitrogen-Doped Hollow Graphene Spheres as a High-Performance Electrocatalyst for Oxygen Reduction Reaction.

Platinum is commonly chosen as an electrocatalyst used for oxygen reduction reaction (ORR). In this study, we report an active catalyst composed of MnO2 nanofilms grown directly on nitrogen-doped hollow graphene spheres, which exhibits high activity toward ORR with positive onset potential (0.94 V vs RHE), large current density (5.2 mA cm-2), and perfect stability. Significantly, when it was used as catalyst for air electrode, a zinc-air battery exhibited a high power density (82 mW cm-2) and specific capacities (744 mA h g-1) comparable to that with Pt/C (20 wt %) as air cathode. The enhanced activity is ascribed to the synergistic interaction between MnO2 and the doped hollow carbon nanomaterials. This easy and cheap method paves a way of synthesizing high-performance electrocatalysts for ORR.

Direct Enrichment of Metallic Single-Walled Carbon Nanotubes by Using NO2 as Oxidant to Selectively Etch Semiconducting Counterparts.

We report an efficient method for enriching high-purity metallic single-walled carbon nanotubes (m-SWCNTs) by using NO2 as oxidant to remove semiconducting components at 220 °C. After etching, m-SWCNTs with purity higher than 90% were obtained. The surviving m-SWCNTs retain an intact structure without any extra defects on their surface.