Bimetallic Cu-Fe catalysts on MXene for synergistically electrocatalytic conversion of nitrate to ammonia.

NO3- is a common water pollutant that can serve as a potential nitrogen source for electrocatalytic NH3 production. However, an efficient and complete removal of low NO3- concentrations remains a challenge. Fe1Cu2@MXene bimetallic catalysts were constructed on two-dimensional Ti3C2Tx MXene carriers via a simple solution-based synthetic method and used for the electrocatalytic reduction of NO3-. The combination of the rich functional groups, high electronic conductivity on the MXene surface, and the synergistic effect between the Cu and Fe sites enabled the composite to effectively catalyse NH3 synthesis, with a 98% conversion of NO3- in 8 h and a selectivity for NH3 of up to 99.6%. In addition, Fe1Cu2@MXene showed excellent environmental and cyclic stability at various pH values and temperatures over multiple (14) cycles. Semiconductor analysis techniques and electrochemical impedance spectroscopy confirmed that the synergistic effect provided by the dual active sites of the bimetallic catalyst enabled fast electron transport. This study provides new insights into the synergistic promotion of NO3- reduction reactions using bimetals.

Coordination Symmetry Breaking of Single-Atom Catalysts for Robust and Efficient Nitrate Electroreduction to Ammonia.

Nitrate electrocatalytic reduction (NO3 RR) for ammonia production is a promising strategy to close the N-cycle from nitration contamination, as well as an alternative to the Haber-Bosch process with less energy consumption and carbon dioxide release. However, current long-term stability of NO3 RR catalysts is usually tens of hours, far from the requirements for industrialization. Here, symmetry-broken Cusingle-atom catalysts are designed, and the catalytic activity is retained after operation for more than 2000 h, while an average ammonia production rate of 27.84 mg h-1 cm-2 at an industrial level current density of 366 mA cm-2 is achieved, obtaining a good balance between catalytic activity and long-term stability. Coordination symmetry breaking is achieved by embedding one Cu atom in graphene nanosheets with two N and two O atoms in the cis-configuration, effectively lowering the coordination symmetry, rendering the active site more polar, and accumulating more NO3 - near the electrocatalyst surface. Additionally, the cis-coordination splits the Cu 3d orbitals, which generates an orbital-symmetry-matched π-complex of the key intermediate *ONH and reduces the energy barrier, compared with the σ-complex generated with other catalysts. These results reveal the critical role of coordination symmetry in single-atom catalysts, prompting the design of more coordination-symmetry-broken electrocatalysts toward possible industrialization.

Built-in Electric Field Triggered Interfacial Accumulation Effect for Efficient Nitrate Removal at Ultra-Low Concentration and Electroreduction to Ammonia.

A built-in electric field in electrocatalyst can significantly accumulate higher concentration of NO3 - ions near electrocatalyst surface region, thus facilitating mass transfer for efficient nitrate removal at ultra-low concentration and electroreduction reaction (NO3 RR). A model electrocatalyst is created by stacking CuCl (111) and rutile TiO2 (110) layers together, in which a built-in electric field induced from the electron transfer from TiO2 to CuCl (CuCl_BEF) is successfully formed . This built-in electric field effectively triggers interfacial accumulation of NO3 - ions around the electrocatalyst. The electric field also raises the energy of key reaction intermediate *NO to lower the energy barrier of the rate determining step. A NH3 product selectivity of 98.6 %, a low NO2 - production of <0.6 %, and mass-specific ammonia production rate of 64.4 h-1 is achieved, which are all the best among studies reported at 100 mg L-1 of nitrate concentration to date.

Surfactant-Free, One-Step Synthesis of Lead-Free Perovskite Hollow Nanospheres for Trace CO Detection.

Owing to their special photoelectric properties, halide perovskites have always attracted research attention. Hollow-structured halide perovskites have many practical applications but are challenging to prepare as most template methods violate their poor chemical and thermal stability. In this study, novel halide perovskite Cs2 PdBr6 hollow nanospheres are prepared using a template-free method; specifically, large quantities of highly pure lead-free halide perovskite Cs2 PdBr6 hollow nanospheres are produced at 30 °C without a surfactant. These ultrapure nanospheres exhibit superiority in chemresistive detection of CO with a detection limit of 50 ppb, which is the lowest among all the reported CO sensing materials. Moreover, in situ sum-frequency-generation spectra and density functional theory calculations reveal that the high sensitivity is attributable to the large specific surface area and surfactant-free surface of rich Br- vacancies that favor CO binding. Overall, this work provides insight on regulation of the halide perovskite structure and the use of hollow spheres in gas-sensing applications.

Surface Functionalization of Single-Layered Ti3C2Tx MXene and Its Application in Multilevel Resistive Memory.

MXenes are a new type of two-dimensional material, and they have attracted extensive attention because of their outstanding conductivity and rich surface functional groups that make surface engineering easy and possible for adapting to diverse applications. However, there are scarce studies on surface engineering of MXene. Herein, we demonstrate for the first time that octylphosphonic acid-modified Ti3C2Tx MXene can be used as an active layer for memory devices and exhibits stable ternary memory behavior. Low threshold voltage, steady retention time, clearly distinguishable resistance states, high ON/OFF rate, OFF/ON1/ON2 = 1:102.7:104.1, and considerable ternary yield (58%) were obtained. In the proof of the mechanism, in situ conductive atomic force microscopy was conducted and the electrode-area relationship was analyzed to demonstrate that charge trapping and filament conduction are more suitable in the nonvolatile information memory of Ti3C2Tx-OP MXene devices. In addition, a polyethylene-terephthalate-based flexible Ti3C2Tx-OP memory device can maintain its stable ternary memory performance after being bent 5000 times. This work provides an easy method for surface modification of MXene and broadens the field of MXene.

One-Step Fabrication of Bio-Compatible Coordination Complex Film on Diverse Substrates for Ternary Flexible Memory.

Recently, resistance random access memories (RRAMs) have been studied extensively, because the demand for information storage is increasing. However, it remains challenging to obtain a flexible device because the active materials involved need to be nontoxic, nonpolluting, distortion-tolerable, and biodegradable as well adhesive to diverse flexible substrates. In this paper, tannic acid (TA) and an iron ion (FeIII ) coordination complex were employed as the active layer in a sandwich-like (Al/active layer/substrate) device to achieve memory performance. A nontoxic, biocompatible TA-FeIII coordination complex was synthesized by a one-step self-assembly solution method. The retention time of the TA-FeIII memory performance was up to 15 000 s, the yield up to 53 %. Furthermore, the TA-FeIII coordination complex can form a high-quality film and shows stable ternary memory behavior on various flexible substrates, such as polyethylene terephthalate (PET), polyimide (PI), printer paper, and leaf. The device can be degraded by immersing it in vinegar solution. Our work will broaden the application of organic coordination complexes in flexible memory devices with diverse substrates.

Mussel-Inspired Polydopamine Coating for Flexible Ternary Resistive Memory.

In recent years, numerous organic molecules and polymers carrying various functional groups were synthesized and used in fabrication of wearable electronic devices. Compared to previous materials that suffer from poisonousness, stiffness and complex film fabrication, we circumvent above matters by taking advantage of mussel-inspired polydopamine as our active material to realize resistive random access memories (RRAMs). Polydopamine thin films were grown on indium tin oxide glass catalyzed by Cu2 SO4 /H2 O2 and characterized by Fourier infrared spectroscopy (FT-IR), UV/Vis spectroscopy and scanning electron microscopy. The Al/Polydopamine film/ITO devices possess ternary memory behavior with good ternary device yield with two threshold voltages around 1.50 V and 3.50 V, long data retention over 104  s of continuous reading or 104 pulse reading. The two resistance switchings are attributed to defects functioning as charge traps and the formation of conductive filaments. A flexible device based on Al/polydopamine film/ITO/polyethylene terephthalate retains its ternary memory behavior after being bent with a bending radius of 1.54 cm and bending cycles up to 5000, demonstrating good compatibility and flexibility of polydopamine.