Conversion of Nitrate to Ammonia by Amidinothiourea-Coordinated Metal Molecular Electrocatalysts with d-π Conjugation.

The electrochemical reduction of nitrate to ammonia (NO3RR) provides a desired alternative of the traditional Haber-Bosch route for ammonia production, igniting a research boom in the development of electrocatalysts with high activity. Among them, molecular electrocatalysts hold considerable promise for the NO3RR, suppressing the competing hydrogen evolution reaction. However, the complicated synthesis procedure, usage of environmentally unfriendly organic solvents, and poor stability of Cu-based molecular electrocatalysts greatly limit their employment in NO3RR, and the development of desired Cu-based molecular catalysts remains challenging. Herein, a simple nonorganic solvent involving a one-step strategy was proposed to synthesize d-π-conjugated molecular electrocatalysts metal-amidinothiourea (M-ATU). Cu-ATU is composed of Cu coordinated with two S and two N atoms, whereas Ni-ATU is formed by Ni with four N atoms from two ATU ligands. Remarkably, Cu-ATU with a Cu-N2S2 coordination configuration exhibits superior NO3RR activity with a NH3 yield rate of 159.8 mg h-1 mgcat-1 (-1.54 V) and Faradaic efficiency of 91.7% (-1.34 V), outperforming previously reported molecular catalysts. Compared to Ni-ATU, Cu-ATU transfers more electrons to the *NO intermediate, effectively breaking the strong sp2 hybridization system and weakening the energy of N═O bonds. The increase in free energy of *NO reduced the energy barriers of the rate-determining step, facilitating the further hydrogenation process over Cu-ATU. Our work opened up a new horizon for exploring molecular electrocatalysts for nitrate activation and paved a way for the in-depth understanding of catalytic behaviors, aligning more closely with industrial demands.

Chemresistive Detection of NO2 of ppb Level in Humid Air at 350 K Using Azo-Spaced Polycroconamide.

Organic molecules are of great interest for gas sensing applications. However, achieving high-performance gas sensors with high sensitivity, fast response, low consumption, and workability in humid conditions is still challenging. Herein, we report the rational design and synthesis of an ion-in-conjugation polymer, PADC (poly-4,4'-azodianiline-croconamide), obtained by the condensation of croconic acid with 4-4'diaminoazobenzene for gas sensing under humid conditions. The as-fabricated PADC-based gas sensor exhibits ultrahigh sensitivity (802.7 ppm-1 at 1 ppm), subppb detection limit, and high selectivity under humid air with an 80% humidity effect at a temperature down to 350 K. PADC shows good planarity, excellent thermostability, and a narrow band gap of 1.2 eV because of azobenzene fragments spacing previously repulsed biphenyl rings. Compared to previous humidity immunity works, PADC-based sensors realized humidity immunity at a relatively lower temperature, resulting in lower energy consumption.

Self-supported spinel nanosphere as bifunctional electrocatalysts for energy-saving hydrogen production via urea-water electrolysis.

Electrochemical oxidation of urea is of great importance in the removal and energy exchange and storage of urea from wastewater as well as of potential applications in potable dialysis of end-stage renal disease. However, the lack of economical electrocatalysts hinders its widespread application. In this study, we successfully fabricated ZnCo2O4 nanospheres with bifunctional catalysis on nickel foam (NF). The catalytic system has high catalytic activity and durability for urea overall electrolysis. The urea oxidation and hydrogen evolution reactions required only 1.32 V and -80.91 mV to obtain ± 10 mA cm-2. Only 1.39 V was needed to obtain 10 mA cm-2 for 40 h without noticeably declining activity. The excellent performance could be attributed to the fact that the material can provide multiple redox couplings and a three-dimensional porous structure to facilitate the release of gases from the surface.

Moisture-Insensitive and Highly Selective Detection of NO2 by Ion-in-Conjugation Covalent Organic Frameworks.

As a common toxic gas, nitrogen dioxide (NO2) seriously threatens the environment and human respiratory system even at part per billion (ppb) level. Covalent organic frameworks (COFs) have gained widespread attention in sensing applications because of the benefits of designability, environmental stability, and a large number of active sites. However, the competitive adsorption of water molecules and the target gas molecules at room temperature as well as the weak interaction between COFs and gas molecules hinder their practical applications. Here, we introduce ion-in-conjugation (IIC) into a covalent organic framework (COF) by preparing a condensate of squaraine (SA) with 1,3,5-tris(4-aminophenyl)benzene (TAPB) to form a mesoporous macrocyclic material (SA-TAPB). Layers of SA-TAPB, drop cast onto interdigitated Ag-Pd alloy electrodes, show a statistically significant conductivity response to NO2 at concentrations as low as 30 ppb and a theoretical detection limit of 10.9 ppb. The sensor displays a lower sensitivity to variations in humidity when operated at 80 °C compared to room temperature. The density functional theory (DFT) calculations indicated that the main adsorption site of NO2 is dual hydrogen bonds formed between two amide hydrogen atoms of SA-TAPB and the NO2 molecule. Gas adsorption experiments revealed that SA-TAPB has the largest adsorption capacity of NO2 versus other interference gases, which were responsible for the excellent selectivity toward NO2.

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.

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.

An Ion-In-Conjugation-Boosted Organic Semiconductor Gas Sensor Operating at High Temperature and Immune to Moisture.

Organic electrical gas sensors have been developed for many decades because of their high sensitivity and selectivity. However, their industrialization is severely hindered by their intrinsic humidity susceptibility and poor recovery. Conventional organic sensory materials can only operate at room temperature owing to their weak intermolecular interactions. Herein, we demonstrate using a croconate polymer (poly-4,4'-biphenylcroconate) that the "ion-in-conjugation" concept enables organic gas sensors to operate at 100 °C and 70 % relative humidity with almost complete recovery. The fabricated sensor had a parts-per-billion (ppb) detection limit for NO2 and showed the highest sensitivity (2526 ppm-1 at 40 ppb) of all reported NO2 chemiresistive sensors. Furthermore, charge transfer increased with temperature. Theoretical calculations and in situ FTIR spectra confirmed the ion-in-conjugation-inspired hydrogen bond as key for excellent sensitivity. A NO2 alarm system was assembled to demonstrate the feasibility of this sensor.

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.

Environmentally Robust Memristor Enabled by Lead-Free Double Perovskite for High-Performance Information Storage.

Memristors are emerging as a rising star of new computing and information storage techniques. However, the practical applications are severely challenged by their instability toward harsh conditions, including high moisture, high temperatures, fire, ionizing irradiation, and mechanical bending. In this work, for the first time, lead-free double perovskite Cs2 AgBiBr6 is utilized for environmentally robust memristors, enabling highly efficient information storage. The memory performance of the typical indium-tin-oxide/Cs2 AgBiBr6 /Au sandwich-like memristors is retained after 1000 switching cycles, 105 s of reading, and 104 times of mechanical bending, comparable to other halide perovskite memristors. Most importantly, the memristive behavior remains robust in harsh environments, including humidity up to 80%, temperatures as high as 453 K, an alcohol burner flame for 10 s, and 60 Co γ-ray irradiation for a dosage of 5 × 105 rad (SI), which is not achieved by any other memristors and commercial flash memory techniques. The realization of an environmentally robust memristor from Cs2 AgBiBr6 with a high memory performance will inspire further development of robust electronics using lead-free double perovskites.

Nanostructured Metal-Organic Conjugated Coordination Polymers with Ligand Tailoring for Superior Rechargeable Energy Storage.

Conjugated coordination polymers have become an emerging category of redox-active materials. Although recent studies heavily focus on the tailoring of metal centers in the complexes to achieve stable electrochemical performance, the effect on different substitutions of the bridging bonds has rarely been studied. An innovative tailoring strategy is presented toward the enhancement of the capacity storage and the stability of metal-organic conjugated coordination polymers. Two nanostructured d-π conjugated compounds, Ni[C6 H2 (NH)4 ]n (Ni-NH) and Ni[C6 H2 (NH)2 S2 ]n (Ni-S), are evaluated and demonstrated to exhibit hybrid electrochemical processes. In particular, Ni-S delivers a high reversible capacity of 1164 mAh g-1 , an ultralong stability up to 1500 cycles, and a fully recharge ability in 67 s. This tailoring strategy provides a guideline to design future effective conjugated coordination-polymer-based electrodes.

Independent Memcapacitive Switching Triggered by Bromide Ion Migration for Quaternary Information Storage.

Memcapacitors are emerging as an attractive candidate for high-density information storage due to their multilevel and adjustable capacitances and long-term retention without a power supply. However, knowledge of their memcapacitive mechanism remains unclear and accounts for the limited implementation of memcapacitors for multilevel memory technologies. Here, repeatable and reproducible quaternary memories fabricated from hybrid perovskite (CH3 NH3 SnBr3 ) memcapacitors are reported. The device can be modulated to at least four capacitive states ranging from 0 to 169 pF with retention for 104 s. Impressively, an effective device yield approaching 100% for quaternary memory switching is achieved by a batch of devices; each state has a sufficiently narrow distribution that can be distinguished from the others and is superior to most multilevel memories that have a low device yield as well as an overlapping distribution of states. The memcapacitive switching stems from the modulated p-i-n junction capacitance triggered by Br- migration, as demonstrated by in situ element mapping, X-ray photoelectron spectra, and frequency-dependent capacitance measurements; this mechanism is different from the widely reported memristive switching involving filamentary conduction. The results provide a new way to produce high-density information storage through memcapacitors.

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.

Detection of NO2 Down to One ppb Using Ion-in-Conjugation-Inspired Polymer.

Nitrogen dioxide (NO2 ) emission has severe impact on human health and the ecological environment and effective monitoring of NO2 requires the detection limit (limit of detection) of several parts-per-billion (ppb). All organic semiconductor-based NO2 sensors fail to reach such a level. In this work, using an ion-in-conjugation inspired-polymer (poly(3,3'-diaminobenzidine-squarine, noted as PDBS) as the sensory material, NO2 can be detected as low as 1 ppb, which is the lowest among all reported organic NO2 sensors. In addition, the sensor has high sensitivity, good reversibility, and long-time stability with a period longer than 120 d. Theoretical calculations reveal that PDBS offers unreacted amine and zwitterionic groups, which can offer both the H-bonding and ion-dipole interaction to NO2 . The moderate binding energies (≈0.6 eV) offer high sensitivity, selectivity as well as good reversibility. The results demonstrate that the ion-in-conjugation can be employed to greatly improve sensitivity and selectivity in organic gas sensors by inducing both H-bonding and ion-dipole attraction.

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.

Pseudohalide-Induced 2D (CH3 NH3 )2 PbI2 (SCN)2 Perovskite for Ternary Resistive Memory with High Performance.

Recently, organic-inorganic hybrid perovskites (OIHP) are studied in memory devices, but ternary resistive memory with three states based on OIHP is not achieved yet. In this work, ternary resistive memory based on hybrid perovskite is achieved with a high device yield (75%), much higher than most organic ternary resistive memories. The pseudohalide-induced 2D (CH3 NH3 )2 PbI2 (SCN)2 perovskite thin film is prepared by using a one-step solution method and fabricated into Al/perovskite film/indium-tin oxide (glass substrate as well as flexible polyethylene terephthalate substrate) random resistive access memory (RRAM) devices. The three states have a conductivity ratio of 1:103 :107 , long retention over 10 000 s, and good endurance properties. The electrode area variation, impedance test, and current-voltage plotting show that the two resistance switches are attributable to the charge trap filling due to the effect of unscreened defect in 2D nanosheets and the formation of conductive filaments, respectively. This work paves way for stable perovskite multilevel RRAMs in ambient atmosphere.

Better Organic Ternary Memory Performance through Self-Assembled Alkyltrichlorosilane Monolayers on Indium Tin Oxide (ITO) Surfaces.

Recently, surface engineering of the indium tin oxide (ITO) electrode of sandwich-like organic electric memory devices was found to effectively improve their memory performances. However, there are few methods to modify the ITO substrates. In this paper, we have successfully prepared alkyltrichlorosilane self-assembled monolayers (SAMs) on ITO substrates, and resistive random access memory devices are fabricated on these surfaces. Compared to the unmodified ITO substrates, organic molecules (i.e., 2-((4-butylphenyl)amino)-4-((4-butylphenyl)iminio)-3-oxocyclobut-1-en-1-olate, SA-Bu) grown on these SAM-modified ITO substrates have rougher surface morphologies but a smaller mosaicity. The organic layer on the SAM-modified ITO further aged to eliminate the crystalline phase diversity. In consequence, the ternary memory yields are effectively improved to approximately 40-47 %. Our results suggest that the insertion of alkyltrichlorosilane self-assembled monolayers could be an efficient method to improve the performance of organic memory devices.

Poly(3,4-ethylenedioxythiophene)-Poly(styrenesulfonate) Interlayer Insertion Enables Organic Quaternary Memory.

Herein, for the first time, quaternary resistive memory based on an organic molecule is achieved via surface engineering. A layer of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) was inserted between the indium tin oxide (ITO) electrode and the organic layer (squaraine, SA-Bu) to form an ITO/PEDOT-PSS/SA-Bu/Al architecture. The modified resistive random-access memory (RRAM) devices achieve quaternary memory switching with the highest yield (∼41%) to date. Surface morphology, crystallinity, and mosaicity of the deposited organic grains are greatly improved after insertion of a PEDOT-PSS interlayer, which provides better contacts at the grain boundaries as well as the electrode/active layer interface. The PEDOT-PSS interlayer also reduces the hole injection barrier from the electrode to the active layer. Thus, the threshold voltage of each switching is greatly reduced, allowing for more quaternary switching in a certain voltage window. Our results provide a simple yet powerful strategy as an alternative to molecular design to achieve organic quaternary resistive memory.

Surface Engineering of ITO Substrates to Improve the Memory Performance of an Asymmetric Conjugated Molecule with a Side Chain.

Organic multilevel random resistive access memory (RRAM) devices with an electrode/organic layer/electrode sandwich-like structure suffer from poor reproducibility, such as low effective ternary device yields and a wide threshold voltage distribution, and improvements through organic material renovation are rather limited. In contrast, engineering of the electrode surfaces rather than molecule design has been demonstrated to boost the performance of organic electronics effectively. Herein, we introduce surface engineering into organic multilevel RRAMs to enhance their ternary memory performance. A new asymmetric conjugated molecule composed of phenothiazine and malononitrile with a side chain (PTZ-PTZO-CN) was fabricated in an indium tin oxide (ITO)/PTZ-PTZO-CN/Al sandwich-like memory device. Modification of the ITO substrate with a phosphonic acid (PA) prior to device fabrication increased the ternary device yield (the ratio of effective ternary device) and narrowed the threshold voltage distribution. The crystallinity analysis revealed that PTZ-PTZO-CN grown on untreated ITO crystallized into two phases. After the surface engineering of ITO, this crystalline ambiguity was eliminated and a sole crystal phase was obtained that was the same as in the powder state. The unified crystal structure and improved grain mosaicity resulted in a lower threshold voltage and, therefore, a higher ternary device yield. Our result demonstrated that PA modification also improved the memory performance of an asymmetric conjugated molecule with a side chain.

Surface engineering to achieve organic ternary memory with a high device yield and improved performance.

Squaraine molecules deposited on indium tin oxide (ITO) substrates modified with phosphonic acids crystalize more orderly than do those on untreated ITO. The as-fabricated electro-resistive memories show the highest ternary device yield observed to date (82%), a narrower switching voltage distribution, and better retention as well as resistance uniformity.

Upgrading Electroresistive Memory from Binary to Ternary Through Single-Atom Substitution in the Molecular Design.

Herein, two molecules based on urea and thiourea, which differ by only a single atom, were designed, successfully synthesized, and fabricated into resistive random-access memory devices (RRAM). The urea-based molecule showed binary write-once-read-many (WORM) storage behavior, whereas the thiourea-based molecule demonstrated ternary storage behavior. Atomic-force microscopy (AFM) and X-ray diffraction (XRD) patterns show that both molecules have smooth morphology and ordered layer-by-layer lamellar packing, which is beneficial for charge transportation and, consequently, device performance. Additionally, the optical and electrochemical properties indicate that the thiourea-based molecule has a lower bandgap and may be polarized by trapped charges, thus the formation of a continuous conductive channel and electric switching occurs at lower bias voltage, which results in ternary WORM behavior. This study, together with our previous work on single-atom substitution, may be useful to tune and improve device performance in the future design of organic memory.