Ternary Eutectic Electrolyte-Assisted Formation and Dynamic Breathing Effect of the Solid-Electrolyte Interphase for High-Stability Aqueous Magnesium-Ion Full Batteries.

Aqueous rechargeable magnesium batteries hold immense potential for intrinsically safe, cost-effective, and sustainable energy storage. However, their viability is constrained by a narrow voltage range and suboptimal compatibility between the electrolyte and electrodes. Herein, we introduce an innovative ternary deep eutectic Mg-ion electrolyte composed of MgCl2·6H2O, acetamide, and urea in a precisely balanced 1:1:7 molar ratio. This formulation was optimized by leveraging competitive solvation effects between Mg2+ ions and two organic components. The full batteries based on this ternary eutectic electrolyte, Mn-doped sodium vanadate (Mn-NVO) anode, and copper hexacyanoferrate cathode exhibited an elevated voltage plateau and high rate capability and showcased stable cycling performance. Ex-situ characterizations unveiled the Mg2+ storage mechanism of Mn-NVO involving initial extraction of Na+ followed by subsequent Mg2+ intercalation/deintercalation. Detailed spectroscopic analyses illuminated the formation of a pivotal solid-electrolyte interphase on the anode surface. Moreover, the solid-electrolyte interphase demonstrated a dynamic adsorption/desorption behavior, referred to as the "breathing effect", which substantially mitigated undesired dissolution and side reactions of electrode materials. These findings underscore the crucial role of rational electrolyte design in fostering the development of a favorable solid-electrolyte interphase that can significantly enhance compatibility between electrode materials and electrolytes, thus propelling advancements in aqueous multivalent-ion batteries.

Pd Decoration with Synergistic High Oxygen Mobility Boosts Hydrogen Sensing Performance at Low Working Temperature on WO3 Nanosheet.

Pd-based materials have received remarkable attention and exhibit excellent H2 sensing performance due to their superior hydrogen storage and catalysis behavior. However, the synergistic effects originated from the decoration of Pd on a metal oxide support to boost the sensing performance are ambiguous, and the deep investigation of metal support interaction (MSI) on the H2 sensing mechanism is still unclear. Here, the model material of Pd nanoparticle-decorated WO3 nanosheet is synthesized, and individual fine structures can be achieved by treating it at different temperatures. Notably, the Pd-WO3-300 materials display superior H2 sensing performance at a low working temperature (110 °C), with a superior sensing response (Ra/Rg = 40.63 to 10 ppm), high sensing selectivity, and anti-interference ability. DFT calculations and detailed structural investigations confirm that the moderate MSI facilitates the generation of high mobility surface O2- (ad) species and a proper ratio of surface Pd0-Pd2+ species, which can significantly boost the desorption of intermediate PdHx species at low temperatures and contribute to enhanced sensing performance. Our work illustrates the effect of MSI on sensing performance and provides insight into the design of advanced sensing materials.

Boosting the sonophotocatalytic performance of BiOCl by Eu doping: DFT and an experimental study.

Bismuth oxychloride (BiOCl) has a unique layered structure and uneven charge distribution, resulting in an internal electric field under polarization, which promotes the efficient separation and migration of photogenerated carriers. BiOCl could be a candidate for sonophotocatalysts. However, the low utilization of visible light limits the application of BiOCl in photocatalysts. In this study, the photocatalytic performance of rare earth element (Nd, Sm, Eu, Er and Er)-doped BiOCl was studied by density functional theory (DFT) and experimentally to screen high-performance catalysts. The band structure, density of states, and optical properties were calculated by the DFT method to predict the photocatalytic activity of rare earth-doped BiOCl. The built-in electric field formed in Eu-doped BiOCl inhibiting electron and hole recombination can be observed. Subsequently, the activity of the photocatalyst and sonophotocatalysts was evaluated. The results show that the photocatalytic and sonophotocatalytic activity of Eu-doped BiOCl is improved, which is consistent with the theoretical prediction. Combining theoretical calculations with experiments, the sonophotocatalytic activity of Eu-doped BiOCl is enhanced, mainly due to the synergistic effect of inhibiting carrier recombination, and expansion to the visible light absorption region.

Alloying of Cu with Ru Enabling the Relay Catalysis for Reduction of Nitrate to Ammonia.

Involving eight electron transfer process and multiple intermediates of nitrate (NO3 - ) reduction reaction leads to a sluggish kinetic and low Faradaic efficiency, therefore, it is essential to get an insight into the reaction mechanism to develop highly efficient electrocatalyst. Herein, a series of reduced-graphene-oxide-supported RuCu alloy catalysts (Rux Cux /rGO) are fabricated and used for the direct reduction of NO3 - to NH3 . It is found that the Ru1 Cu10 /rGO shows the ammonia formation rate of 0.38 mmol cm-2 h-1 (loading 1 mg cm-2 ) and the ammonia Faradaic efficiency of 98% under an ultralow potential of -0.05 V versus Reversible Hydrogen Electode (RHE), which is comparable to Ru catalyst. The highly efficient activity of Ru1 Cu10 /rGO can be attributed to the synergetic effect between Ru and Cu sites via a relay catalysis, in which the Cu shows the exclusively efficient activity for the reduction of NO3 - to NO2 - and Ru exhibits the superior activity for NO2 - to NH3 . In addition, the doping of Ru into Cu tunes the d-band center of alloy and effectively modulates the adsorption energy of the NO3 - and NO2 - , which promotes the direct reduction of NO3 - to NH3 . This synergetic electrocatalysis strategy opens a new avenue for developing highly efficient multifunctional catalysts.

High n-type and p-type conductivities and power factors achieved in a single conjugated polymer.

The charge transport properties of conjugated polymers are commonly limited by the energetic disorder. Recently, several amorphous conjugated polymers with planar backbone conformations and low energetic disorder have been investigated for applications in field-effect transistors and thermoelectrics. However, there is a lack of strategy to finely tune the interchain π-π contacts of these polymers that severely restricts the energetic disorder of interchain charge transport. Here, we demonstrate that it is feasible to achieve excellent conductivity and thermoelectric performance in polymers based on thiophene-fused benzodifurandione oligo(p-phenylenevinylene) through reducing the crystallization rate of side chains and, in this way, carefully controlling the degree of interchain π-π contacts. N-type (p-type) conductivities of more than 100 S cm-1 (400 S cm-1) and power factors of more than 200 µW m-1 K-2 (100 µW m-1 K-2) were achieved within a single polymer doped by different dopants. It further demonstrated the state-of-the-art power output of the first flexible single-polymer thermoelectric generator.

BiOCl Heterojunction photocatalyst: Construction, photocatalytic performance, and applications.

BiOCl semiconductors have attracted extensive amounts of attention and have substantial potential in alleviating energy shortages, improving sterilization performance, and solving environmental issues. To improve the optical quantum efficiency of layered BiOCl, the lifetimes of photogenerated electron-hole pairs, and BiOCl reduction capacity. During the past decade, researchers have designed many effective methods to weaken the effects of these limitations, and heterojunction construction is regarded as one of the most promising strategies. In this paper, BiOCl heterojunction photocatalysts designed and synthesized by various research groups in recent years were reviewed, and their photocatalytic properties were tested. Among them, direct Z-scheme and S-scheme photocatalysts have high redox potentials and intense redox capabilities. Hence, they exhibit excellent photocatalytic activity. Furthermore, the applications of BiOCl heterojunctions for pollutant degradation, CO2 reduction, water splitting, N2 fixation, organic synthesis, and tumor ablation are also reviewed. Finally, we summarize research on the BiOCl heterojunctions and put forth new insights on overcoming their present limitations.

Ultra-sensitive H2S sensor based on sunflower-like In-doped ZnO with enriched oxygen vacancies.

Metal oxide sensors face the challenge of high response and fast recovery at low operating temperatures for the detection of toxic and flammable hydrogen sulfide (H2S) gases. Herein, novel In-doped ZnO with a sunflower-like structure and tunable surface properties was rationally synthesized. The substitutional In atom in the ZnO crystal can dramatically enhance the concentration of oxygen vacancies (Ov), the In-ZnO sites are responsible for fast recovery, and the formation of sub-stable sulfide intermediates gives rise to the high response towards H2S. As a result, the response of the optimized 4In-ZnO sensor is 3538.36 to 50 ppm H2S at a low operating temperature of 110 °C, which is 106 times higher than that of pristine ZnO. Moreover, the response time and recovery time to 50 ppm H2S are 100 s and 27 s, respectively, with high selectivity and stability. First-principles calculations revealed that 4In-ZnO with rich Ov exhibited higher adsorption energy for the H2S molecule than pristine ZnO, resulting in effortless H2S detection. Our work lays the foundation for the rational design of highly sensitive gas sensors through precise doping of atoms in oxygen-rich vacancies in semiconductor materials.

Two Structurally Similar Co5 Cluster-Based Metal-Organic Frameworks Containing Open Metal Sites for Efficient C2H2/CO2 Separation.

To reasonably design and synthesize metal-organic frameworks (MOFs) with high stability and excellent adsorption/separation performance, the pore configuration and functional sites are very important. Here, we report two structurally similar cluster-based MOFs using a pyridine-modified low-symmetry ligand [H4L = 2,6-bis(2',5'-dicarboxyphenyl)pyridine], [(NH2Me2)2][Co5(L)2(OCH3)2(µ3-OH)2·2DMF]·2DMF·2H2O (1) and [Co5(L)2(µ3-OH)2(H2O)2]·2H2O·4DMF (2). The structures of 1 and 2 are built from Co5 clusters, which have one-dimensional open channels, but their microporous environments are different due to the different ways in which ligands bind to the metals. Both MOFs have extremely high chemical stabilities over a wide pH range (2-12). The two MOFs have similar adsorption capacities of C2H2 (144.0 cm3 g-1 for 1 and 141.3 cm3 g-1 for 2), but 1 has a higher C2H2/CO2 selectivity of 3.5 under ambient conditions. The difference in gas adsorption and separation between the two MOFs has been compared by a breakthrough experiment and theoretical calculation, and the influence of the microporous environment on the gas adsorption and separation performance of MOFs has been further studied.

Molecular-Level Zn-Ion Transfer Pump Specifically Functioning on (002) Facets Enables Durable Zn Anodes.

The modification of metallic Zn anode contributes to solving the cycling issue of Zn-ion batteries (ZIBs) by restraining the dendrite growth and side reactions. In this regard, modulating (002) Zn is an effective way to prolong the lifespan of ZIBs with a parallel arrangement of Zn deposition. Herein, the authors propose to add trace amounts of Zn(BF4 )2 additive in 3 M ZnSO4 to promote in-plane Zn deposition by forming a BF4 - -[Zn(H2 O)6 ]2+ -[Zn(BF4 )3 ]- transfer process and specifically functioning on (002) facets. In this way, the optimized electrolyte highly boosts the cycling stability of Zn anodes with a long lifespan at 34.2% Zn utilization (500 h/10 mA cm-2 ) and 51.3% Zn utilization (360 h/10 mA cm-2 ; 834 h/1 mA cm-2 ). Moreover, the electroplated Zn on Cu substrate exhibits a competitive cumulative plating capacity (CPC) of 2.87 Ah cm-2 under harsh conditions. The assembled Zn|(NH4 )2 V6 O16 ·3H2 O full cells with a high cathode loading of 29.12 mg cm-2 also realizes almost no capacity degradation even after 2000 cycles at 2 A g-1 . With this cost-effective strategy, it is promising to push the development of aqueous ZIBs as well as provide inspiration for metal anode optimization in other energy storage systems.

Light-responsive self-strained organic semiconductor for large flexible OFET sensing array.

With the wide application of organic semiconductors (OSCs), researchers are now grappling with a new challenge: design and synthesize OSCs materials with specific functions to satisfy the requirements of high-performance semiconductor devices. Strain engineering is an effective method to improve the semiconductor material's carrier mobility, which is fundamentally originated from the rearrangement of the atomic packing model of materials under mechanic stress. Here, we design and synthesize a new OSC material named AZO-BTBT-8 based on high-mobility benzo[b]benzo[4,5]thieno[2,3-d]thiophene (BTBT) as the semiconductor backbone. Octane is employed to increase molecular flexibility and solubility, and azobenzene at the other end of the BTBT backbone provides photoisomerization properties and structural balance. Notably, the AZO-BTBT-8 photoisomerization leads to lattice strain in thin-film devices, where exceptional device performance enhancement is realized. On this basis, a large-scale flexible organic field-effect transistor (OFET) device array is fabricated and realizes high-resolution UV imaging with reversible light response.

Cocrystallization Enabled Spatial Self-Confinement Approach to Synthesize Crystalline Porous Metal Oxide Nanosheets for Gas Sensing.

Crystalline metal oxide nanosheets show exceptional catalytic performance owing to the large surface-to-volume ratio and quantum confinement effect. However, it is still a challenge to develop a facile and general method to synthesize metal oxide nanosheets. Herein, we report a cocrystallization induced spatial self-confinement approach to synthesize metal oxide nanosheets. Taking the synthesis of SnO2 as an example, the solvent evaporation from KCl and SnCl2 solution induces the cocrystallization of KCl and K2 SnCl6 , and the obtained composite with encapsulated K2 SnCl6 can be in situ converted into SnO2 nanosheets confined in KCl matrix, after water washing to remove KCl, porous SnO2 nanosheets can be obtained. Notably, a series of metal oxide nanosheets can be obtained through this general and efficient green route. In particular, porous CeO2 /SnO2 nanosheets with improved surface O- species and abundant oxygen vacancies exhibit superior gas sensing performance to 3-hydroxy-2-butanone.

Regulating Interfacial Desolvation and Deposition Kinetics Enables Durable Zn Anodes with Ultrahigh Utilization of 80.

Rechargeable aqueous zinc ion batteries (ZIBs) represent a promising technology for large-scale energy storage due to their high capacity, intrinsic safety and low cost. However, Zn anodes suffer from poor reversibility and cycling stability caused by the side-reactions and dendrite issues, which limit the Zn utilization in the ZIBs. Herein, to improve the durability of Zn under high utilization, an aluminum-doped zinc oxide (AZO) interphase is presented. The AZO interphase inhibits side reactions by isolating active Zn from the bulk electrolyte, and enables facile and uniform Zn deposition kinetics by accelerating the desolvation of hydrated Zn2+ and homogenizing the electric field distribution. Accordingly, the AZO-coated Zn (AZO@Zn) anode exhibits a long lifespan of 600 h with Zn utilization of 34.1% at the current density of 10 mA cm-2 . Notably, even under ultrahigh Zn utilization of 80%, the AZO@Zn remains stable cycling over 200 h. Meanwhile, the V2 O5 /AZO@Zn full cell with limited Zn excess displays high capacity retention of 86.8% over 500 cycles at 2 A g-1 . This work provides a simple and efficient strategy to ensure the reversibility and durability of Zn anodes under high utilization conditions, holding a great promise for commercially available ZIBs with competitive energy density.

An AIE-Active Ultrathin Polymeric Self-Assembled Monolayer Sensor for Trace Volatile Explosive Detection.

This work has prepared polymeric self-assembled monolayer (SAM) sensors for the detection of trace volatile nitroaromatic compound (NAC) explosives by fluorescence quenching. A typical aggregation-induced emission (AIE) luminogen 1,1,2,2-tetraphenylethene (TPE) polymerizes into PTPE to increase the fluorescence intensity in the SAMs, and the phosphoric acid acts as the anchor group to form stable covalent bonds with the Al2 O3 substrate. This design takes advantage of the high sensitivity and good stability of SAMs, and high fluorescence intensity, and "wire effect" of the conjugated polymers. The polymeric SAM sensors are prepared on the Al2 O3 silicon wafer and testing paper. Both of them show good response speed, reversibility, selectivity, and sensitivity. The detection limits down to 0.07, 0.35, and 4.11 ppm for TNT, DNB, and NB, respectively, are achieved on the inorganic testing paper. Furthermore, due to the higher fluorescence intensity by interlacing and overlapping of fibers, the detection of the paper can be distinguished by naked eyes even with a low-power handheld UV lamp, which provides an experimental basis for the development of cheap and easy trace NAC explosive sensors.

Fast-Scanning Chip-Calorimetry Measurement of Crystallization Kinetics of Poly(Glycolic Acid).

We report fast-scanning chip-calorimetry measurement of isothermal crystallization kinetics of poly(glycolic acid) (PGA) in a broad temperature range. We observed that PGA crystallization could be suppressed by cooling rates beyond -100 K s-1 and, after fast cooling, by heating rates beyond 50 K s-1. In addition, the parabolic curve of crystallization half-time versus crystallization temperature shows that PGA crystallizes the fastest at 130 °C with the minimum crystallization half-time of 4.28 s. We compared our results to those of poly(L-lactic acid) (PLLA) with nearby molecular weights previously reported by Androsch et al. We found that PGA crystallizes generally more quickly than PLLA. In comparison to PLLA, PGA has a much smaller hydrogen side group than the methyl side group in PLLA; therefore, crystal nucleation is favored by the higher molecular mobility of PGA in the low temperature region as well as by the denser molecular packing of PGA in the high temperature region, and the two factors together decide the higher crystallization rates of PGA in the whole temperature range.

A Formaldehyde Sensor Based on Self-Assembled Monolayers of Oxidized Thiophene Derivatives.

High-performance formaldehyde sensors play an important role in air quality assessment. Herein, a self-assembled monolayer (SAM) sensor for trace formaldehyde (FA) is fabricated based on the fluorescence enhancement of oxidized thiophene derivatives. In the primary SAM molecules, the functional backbone trithiophene (3T) links to the anchor through an n-propyl group. The anchor with an active Si-Cl bond can form a covalent bond with the SiO2 substrate by solution incubation, which ensures good stability against organic solvents and high sensitivity via monolayer structures. With the alkyl chain's leading, a dense 3T SAM can be obtained on SiO2. Upon exposure to UV light in the presence of oxygen, 3T can be oxidized into a nonfluorescent but coordination-active product with abundant carbonyl groups, which can be doped with FA and induce a blueshifted fluorescence. With this mechanism, we proposed an SAM-based FA sensor by detecting the enhancement of the blueshifted fluorescence. Reliable reversibility, selectivity, stability, and detection limit lower than 1 ppm are achieved in this system. The work provides an experimental basis for developing a cheap, efficient, and flexible sensor for trace FA detection.

Template-Directed Bifunctional Dodecahedral CoP/CN@MoS2 Electrocatalyst for High Efficient Water Splitting.

Designing high efficient and noble metal-free bifunctional electrocatalysts for both hydrogen and oxygen generation is still critical and challenged. In this study, hierarchical dodecahedral-structured CoP/CN@MoS2 is prepared through a two-step calcination treatment and a solvothermal approach. The metal-organic framework of ZIF-67 is chosen to serve as the template and for providing Co sources, in which ZIF-67 is first transformed to Co nanoparticles embedded in nitrogen-doped carbon polyhedrons and then transformed to CoP/CN. MoS2 nanosheets are further grown on the surface of dodecahedral-structured CoP/CN with a solvothermal method. Benefiting from the synergistic coupling effect of CoP and MoS2 and the nitrogen-doped carbon matrix, advanced hydrogen evolution reaction (HER) both in acid and alkaline solution as well as splendid oxygen evolution reaction (OER) performance in alkaline aqueous were achieved. Moreover, the coupling effect of CoP/CN and MoS2 is disclosed theoretically by density functional theory calculations to validate the increased HER activity. The as-prepared hybrid CoP/CN@MoS2 not only exhibits decent HER activity in acidic (η10 = 144 mV) and alkaline solutions (η10 = 149 mV), but also exhibits splendid OER activity (η10 = 289 mV) in 1.0 M KOH. This work represents a solid step toward boosting the electrocatalytic kinetics of nonprecious catalysts.

High selective detection of mercury (II) ions by thioether side groups on metal-organic frameworks.

Mercury ions can significantly affect the organism and environment even at a very low concentration. Thus, great efforts have been devoted to developing high sensitive electrochemical sensors, especially the one that not only detect the mercury ions but also effective sensitive to thymine-Hg2+-thymine in aqueous solution. Metal-organic-frameworks (MOFs) possess hollow nature and are easy for grafting functional groups, however, there is still no attempts for working as electrochemical sensors in detecting mercury ions. Herein, we report a novel type sensor of Zr(IV)-based MOFs with specifically attached thioether side groups allowing mercury ions to be easily adsorbed and detected. The Zr(IV)-involved MOFs show strong binding to mercury ions compared with the bare MOFs, as confirmed by both experiment measurements and theoretical calculations. The as-prepared senor is sensitive ranging from 0.01 nM to 3 µM with detection limitation of 7.3 fM, which is better than most of T-Hg2+-T- and enzyme-based sensors reported so far. The high sensitivity could be due to the straightforward adsorption pathway and the biomolecule exclusion nature of the Zr(IV)-involved MOFs sensor. We anticipate that our findings could pave the way for MOFs-based sensor exploration towards its commercial applications.

Correction to: A glassy carbon electrode modified with N-doped carbon dots for improved detection of hydrogen peroxide and paracetamol.

The authors of "A glassy carbon electrode modified with N-doped carbon dots for improved detection of hydrogen peroxide and paracetamol (Microchimica Acta 185, no. 2 (2018): 87)" wish to replace the incorrect images of Fig. 1C, 1D shown below.

Electronic and Magnetic Properties of Stone⁻Wales Defected Graphene Decorated with the Half-Metallocene of M (M = Fe, Co, Ni): A First Principle Study.

The geometrical, electronic structure, and magnetic properties of the half-metallocene of M (M = Fe, Co, Ni) adsorbed on Stone⁻Wales defected graphene (SWG) were studied using the density functional theory (DFT), aiming to tune the band structure of SWG. The introduction of cyclopentadienyl (Cp) and half-metallocene strongly affected the band structure of SWG. The magnetic properties of the complex systems originated from the 3D orbitals of M (M = Fe, Co, Ni), the molecular orbital of Cp, and SWG. This phenomenon was different from that found in a previous study, which was due to metal ion-induced sandwich complexes. The results have potential applications in the design of electronic devices based on SWG.

A glassy carbon electrode modified with N-doped carbon dots for improved detection of hydrogen peroxide and paracetamol.

Nitrogen doped carbon dots (NCDs) were synthesized using a low temperature approach and used to modify a glassy carbon electrode (GCE) via dipping. The oxygen groups on the surface of the NCDs, and the charge delocalization of the NCDs warrant an excellent electrocatalytic activity of the GCE toward oxidation of paracetamol (PA) and reduction of H2O2. PA and H2O2 were detected at 0.34 V and -0.4 V (both vs. Ag/AgCl) using differential pulse voltammetry and amperometric I-T measurement, respectively. The modified GCE has a linear response to PA in the 0.5 to 600 µM concentration range, and to H2O2 in the 0.05 µM to 2.25 mM concentration range. The detection limits are 157 nM and 41 nM, respectively. In our perception, the modified GCE holds promise for stable, selective and sensitive determination of PA and H2O2 in pharmaceutical analysis. Graphic abstract Nitrogen doped carbon dots (NCDs) were synthesized and used to modify a glassy carbon electrode. Surface functional groups on NCDs can trigger electrocatalytic reactions toward paracetamol oxidation and H2O2 reduction with high sensitivities.