Revealing the synergistic effect of Ni single atoms and adjacent 3d metal doped Ni nanoparticles in electrocatalytic CO2 reduction.

Herein, we report the successful fabrication of a series of transition metal doped Ni nanoparticles (NPs) coordinated with Ni single atoms in nitrogen-doped carbon nanotubes (denoted as Ni1+NPsM-NCNTs, M = Mn, Fe, Co, Cu and Zn; Ni1 = Ni single atom). X-ray absorption fine structure reveals the coexistence of Ni single atoms with Ni-N4 coordination and NiM NPs. When applied for electrocatalytic CO2RR, the Ni1+NPsM-NCNT compounds show the Faradaic efficiency of CO (FECO) with a volcano-like tendency of Mn < Fe ≈ Co < Zn < Cu, in which the Ni1+NPsCu-NCNT exhibits the highest FECO of 96.92%, a current density of 171.25 mA cm-2 and a sustainable stability over 24 hours at a current density of 100 mA cm-2, outperforming most reported examples in the literature. Detailed experiments and theoretical calculations reveal that for Ni1+NPsCu-NCNTs, the electron transfer from NiCu NPs to Ni single atoms strengthens the adsorption of *COOH intermediates. Moreover, the d-band center of Ni-N in Ni1+NPsCu-NCNT is upshifted, providing stronger binding with the reaction intermediates of *COOH, whereas the NiCu NPs increase the Gibbs free energy change of the Volmer step, suppressing the competitive HER.

Directional Activation of Oxygen by the Au-Loaded ZnAl-LDH with Defect Structure for Highly Efficient Photocatalytic Oxidative Coupling of Methane.

Photocatalytic oxidative coupling of CH4 (OCM) is a promising CH4 conversion process that can achieve efficient methane conversion with the assistance of O2 . It remains to be highly challenging to improve the photocatalytic OCM activity from catalyst design and to deepen the understanding of the reactant activation in the OCM process. In this work, the Au-loaded ZnAl-layered double hydroxides (LDHs) with and without oxygen vacancy are constructed (denoted as Au/ZnAl and Au/ZnAl-v), respectively. When applied for photocatalytic OCM, the Au/ZnAl-v shows a CH4 conversion rate of 8.5 mmol g-1 h-1 with 92% selectivity of C2 H6 at 40 °C, outperforming most reported photocatalytic OCM systems at low temperature reported in the literature. Furthermore, the catalytic performance of Au/ZnAl-v can be stable for 100 h. In contrast, the An/ZnAl exhibits a CH4 conversion rate of 0.8 mmol g-1 h-1 with 46% selectivity of C2 H6 . Detailed characterizations and DFT calculation studies reveal that the introduced Ov sites on Au/ZnAl-v are able to activate O2 , and the resulting superoxide radical O2 ·- greatly promotes the activation of CH4 . The coupling of CH3 · groups with the assistance of Au cocatalyst leads to the formation of C2 H6 with high photocatalytic activity.

Self-Assembly of Polyoxometalate-Based Nanoparticle Surfactants in Solutions.

Nanoparticle surfactants (NPSs) are an emergent class of amphiphiles attractive for their controllable assembly at the liquid-liquid interface. In this work, intriguing self-assembly behavior and stimuli-responsiveness of NPSs in homogeneous solutions are presented. With ß-cyclodextrin-grafted polyoxometalates (POMs) and ferrocene (or azobenzene)-terminated polystyrene in water/tetrahydrofuran, POM-based NPSs are formed via host-guest interactions and self-organize to vesicles driven by solvent-phobic effects. The tunable supramolecular interactions allow these assemblies to be responsive to redox or light stimulus, respectively, affording an on-demand assembly/disassembly capacity that shows promise in delivery and release applications.

Interfacial Preparation of Polyoxometalate-Based Hybrid Supramolecular Polymers by Orthogonal Self-Assembly.

The construction of organic-inorganic hybrid supramolecular polymers using polyoxometalate (POM) as building block is expected to bring new opportunities to the functionalization of supramolecular polymers and the development of novel POM-based soft materials. Here, by using the orthogonal self-assembly based on host-guest interactions and metal-ligand interactions, we report the in situ construction of a novel POM-based hybrid supramolecular polymer (POM-SP) at the oil-water interface, while the redox and competitive responsiveness can be triggered independently. Moreover, the binding energy of POM-SP at the interface is sufficiently strong so that the assembly of POM-SP jams, allowing the stabilization of liquids in nonequilibrium shapes, offering the possibility of fabricating all-liquid constructs with reconfigurability.

A pseudo-Double-Network Hydrogel Built upon Layered Double Hydroxides with Self-Strengthening Properties.

While great achievements have been made in the development of mechanically robust nanocomposite hydrogels, incorporating multiple interactions on the bases of two demensional inorganic cross-linkers to construct self-strengthening hydrogels has rarely been investigated. To this end, we propose here a new method for the coupling the dynamic covalent bonds and non-covalent interactions within a pseudo double-network system. The pseudo first network, formed through the Schiff Base reation between Tris-modified layered double hydroxides (Tris-LDHs) and oxidized dextran (ODex), is linked to the second network built upon non-covalent interactions between Tris-LDHs and poly(acrylamide-co-2-acrylamido-2-methyl-propanesulfonate) (p-(AM-co-AMPS). The swelling and mechanical properties of the resulting hydrogels have been investigated as a function of the ODex and AMPS contents. The as-prepared hydrogel can swell to 420 times of its original size and retain more than 99.9 wt.% of water. Mechanical tests show that the hydrogel can bear 90 % of compression and is able to be stretched to near 30 times of its original length. Cyclic tensile tests reveal that the hydrogels are capable of self-strengthening after mechanical training. The unique energy dissipation mechanism based on the dynamic covalent and non-covalent interactions is considered to be responsible for the outstanding swelling and mechanical performances.

Polyoxometalates as Potential Artificial Enzymes toward Biological Applications.

Artificial enzymes, as alternatives to natural enzymes, have attracted enormous attention in the fields of catalysis, biosensing, diagnostics, and therapeutics because of their high stability and low cost. Polyoxometalates (POMs), a class of inorganic metal oxides, have recently shown great potential in mimicking enzyme activity due to their well-defined structure, tunable composition, high catalytic efficiency, and easy storage properties. This review focuses on the recent advances in POM-based artificial enzymes. Different types of POMs and their derivatives-based mimetic enzyme functions are covered, as well as the corresponding catalytic mechanisms (where available). An overview of the broad applications of representative POM-based artificial enzymes from biosensing to theragnostic is provided. Insight into the current challenges and the future directions for POMs-based artificial enzymes is discussed.

Ultrathin NiV Layered Double Hydroxide for Methanol Electrooxidation: Understanding the Proton Detachment Kinetics and Methanol Dehydrogenation Oxidation.

Electrochemical methanol oxidation reaction (MOR) is regarded as a promising pathway to obtain value-added chemicals and drive cathodic H2 production, while the rational design of catalyst and in-depth understanding of the structure-activity relationship remains challenging. Herein, the ultrathin NiV-LDH (u-NiV-LDH) with abundant defects is successfully synthesized, and the defect-enriched structure is finely determined by X-ray adsorption fine structure etc. When applied for MOR, the as-prepared u-NiV-LDH presents a low potential of 1.41 V versus RHE at 100 mA cm-2, which is much lower than that of bulk NiV-LDH (1.75 V vs RHE) at the same current density. The yield of H2 and formate is 98.2% and 88.1% as its initial over five cycles and the ultrathin structure of u-NiV-LDH can be well maintained. Various operando experiments and theoretical calculations prove that the few-layer stacking structure makes u-NiV-LDH free from the interlayer hydrogen diffusion process and the hydrogen can be directly detached from LDH laminate. Moreover, the abundant surface defects upshift the d-band center of u-NiV-LDH and endow a higher local methanol concentration, resulting in an accelerated dehydrogenation kinetics on u-NiV-LDH. The synergy of the proton detachment from the laminate and the methanol dehydrogenation oxidation contributes to the excellent MOR performance of u-NiV-LDH.

Recent Progress of Remediating Heavy Metal Contaminated Soil Using Layered Double Hydroxides as Super-Stable Mineralizer.

Heavy metal contamination in soil, which is harmful to both ecosystem and mankind, has attracted worldwide attention from the academic and industrial communities. However, the most-widely used remediation technologies such as electrochemistry, elution, and phytoremediation. suffer from either secondary pollution, long cycle time or high cost. In contrast, in situ mineralization technology shows great potential due to its universality, durability and economical efficiency. As such, the development of mineralizers with both high efficiency and low-cost is the core of in situmineralization. In 2021, the concept of 'Super-Stable Mineralization' was proposed for the first time by Kong et al.[1] The layered double hydroxides (denoted as LDHs), with the unique host-guest intercalated structure and multiple interactions between the host laminate and the guest anions, are considered as an ideal class of materials for super-stable mineralization. In this review, we systematically summarize the application of LDHs in the treatment of heavy metal contaminated soil from the view of: 1) the structure-activity relationship of LDHs in in situ mineralization, 2) the advantages of LDHs in mineralizing heavy metals, 3) the scale-up preparation of LDHs-based mineralizers and 4) the practical application of LDHs in treating contaminated soil. At last, we highlight the challenges and opportunities for the rational design of LDH-based mineralizer in the future.

Recent Advances in the Study of Trivalent Lanthanides and Actinides by Phosphinic and Thiophosphinic Ligands in Condensed Phases.

The separation of trivalent actinides and lanthanides is a key step in the sustainable development of nuclear energy, and it is currently mainly realized via liquid-liquid extraction techniques. The underlying mechanism is complicated and remains ambiguous, which hinders the further development of extraction. Herein, to better understand the mechanism of the extraction, the contributing factors for the extraction are discussed (specifically, the sulfur-donating ligand, Cyanex301) by combing molecular dynamics simulations and experiments. This work is expected to contribute to improve our systematic understanding on a molecular scale of the extraction of lanthanides and actinides, and to assist in the extensive studies on the design and optimization of novel ligands with improved performance.

Laser-Triggered High Graphitization of Mo2C@C: High Rate Performance and Excellent Cycling Stability as Anode of Lithium Ion Batteries.

Fast electron/ion transport and cycling stability of anode materials are key factors for achieving a high rate performance of battery materials. Herein, we successfully fabricated a carbon-coated Mo2C nanofiber (denoted as laser Mo2C@C) as the lithium ion battery anode material by laser carbonization of PAN-PMo12 (PAN = Polyacrylonitrile; PMo12 = H3PMo12O40). The highly graphitized carbon layer in laser Mo2C@C effectively protects Mo2C from agglomeration and flaking while facilitating electron transfer. As such, the laser Mo2C@C electrode displays an excellent electrochemical stability under 5 A g-1, with a capacity up to 300 mA h g-1 after 3000 cycles. Furthermore, the extended X-ray absorption fine structure results show the existence of some Mo vacancies in Mo2C@C. Density functional theory calculations further prove that such vacancies make the defective Mo2C@C composites energetically more favorable for lithium storage in comparison with the intact Mo2C.

Pd Loaded NiCo Hydroxides for Biomass Electrooxidation: Understanding the Synergistic Effect of Proton Deintercalation and Adsorption Kinetics.

The key issue in the 5-hydroxymethylfurfural oxidation reaction (HMFOR) is to understand the synergistic mechanism involving the protons deintercalation of catalyst and the adsorption of the substrate. In this study, a Pd/NiCo catalyst was fabricated by modifying Pd clusters onto a Co-doped Ni(OH)2 support, in which the introduction of Co induced lattice distortion and optimized the energy band structure of Ni sites, while the Pd clusters with an average size of 1.96 nm exhibited electronic interactions with NiCo support, resulting in electron transfer from Pd to Ni sites. The resulting Pd/NiCo exhibited low onset potential of 1.32 V and achieved a current density of 50 mA/cm2 at only 1.38 V. Compared to unmodified Ni(OH)2 , the Pd/NiCo achieved an 8.3-fold increase in peak current density. DFT calculations and in situ XAFS revealed that the Co sites affected the conformation and band structure of neighboring Ni sites through CoO6 octahedral distortion, reducing the proton deintercalation potential of Pd/NiCo and promoting the production of Ni3+ -O active species accordingly. The involvement of Pd decreased the electronic transfer impedance, and thereby accelerated Ni3+ -O formation. Moreover, the Pd clusters enhanced the adsorption of HMF through orbital hybridization, kinetically promoting the contact and reaction of HMF with Ni3+ -O.

Photocatalytic Oxidative Coupling of Ethane to n-Butane Using CO2 as a Soft Oxidant over NiTi-Layered Double Hydroxide.

Selective conversion of ethane (C2 H6 ) to high-value-added chemicals is a very important chemical process, yet it remains challenging owing to the difficulty of ethane activation. Here, a NiTi-layered double hydroxide (NiTi-LDH) photocatalyst is reported for oxidative coupling of ethane to n-butane (n-C4 H10 ) by using CO2 as an oxidant. Remarkably, the as-prepared NiTi-LDH exhibits a high selectivity for n-C4 H10 (92.35%) with a production rate of 62.06 µmol g-1 h-1 when the feed gas (CO2 /C2 H6 ) ratio is 2:8. The X-ray absorption fine structure (XAFS) and photoelectron characterizations demonstrate that NiTi-LDH possesses rich vacancies and high electron-hole separation efficiency, which can promote the coupling of C2 H6 to n-C4 H10 . More importantly, density functional theory (DFT) calculations reveal that ethane is first activated on the oxygen vacancies of the catalyst surface, and the C─C coupling pathway is more favorable than the C─H cleavage to C2 H4 or CH4 , resulting in the high production rate and selectivity for n-C4 H10 .

Coexistence of Au single atoms and Au nanoparticles on NiAl-LDH for selective electrooxidation of benzyl alcohol to benzaldehyde.

Introducing different active sites into heterogeneous catalysts provides new prospects to address the challenges in single-atom catalysis. Herein, the Au single atoms together and the Au nanoparticles were loaded onto NiAl-LDH by a facile impregnation-reduction method for the first time, resulting in the formation of Au1+n-NiAl-LDH, in which abundant Au single atoms are located around the Au nanoparticles with ∼5 nm size. When applied in the electrocatalytic benzyl alcohol oxidation reaction (BAOR), the as-prepared Au1+n-NiAl-LDH exhibits a remarkable selectivity of 91% and 177.63 µmol for benzaldehyde in 5 hours, while in contrast examples using solely Au single atom loaded NiAl-LDH (Au1-NiAl-LDH) and solely Au nanoparticle loaded NiAl-LDH (Aun-NiAl-LDH) can only realize 87.36 µmol production (75% selectivity) and 48.90 µmol production (28% selectivity) of benzaldehyde, respectively. Such a dramatic difference can be attributed to the synergistic effects of Au single atoms and Au nanoparticles. DFT calculation results reveal that for Au1+n-NiAl-LDH, Au single atoms promote the dehydrogenation capacity of LDH laminates, while Au nanoparticles offer adsorption sites for the electrophilic attachment of benzyl alcohol.

Vanadium-Substituted Polyoxometalates Regulate Prion Protein Fragment 106-126 Misfolding by an Oxidation Strategy.

Prion disorders are a group of lethal infectious neurodegenerative diseases caused by the spontaneous aggregation of misfolded prion proteins (PrPSc). The oxidation of such proteins by chemical reagents can significantly modulate their aggregation behavior. Herein, we exploit a series of vanadium-substituted Keggin-type tungsten and molybdenum POMs (W- and Mo-POMs) as chemical tools to oxidize PrP106-126 (denoted as PrP), an ideal model for studying PrPSc. Due to the band gaps being larger than that of Mo-POMs, W-POMs possess higher structural stability and show stronger binding and oxidation effect on PrP. Additionally, the substitution of W/Mo by vanadium elevates the local electron distribution on the bridged O(26) atom, thereby strengthening the hydrogen bonding of POMs with the histidine site. Most importantly, with the number of substituted vanadium increases, the LUMO energy level of POMs decreases, making it easier to accept electrons from methionine. As a result, PW10V2 displays the strongest oxidation on the methionine residue of PrP, leading to an excellent inhibitory effect on PrP aggregation and a significant attenuation on its neurotoxicity.

Insight into the In-Situ Encapsulation-Reassembly Strategy To Fabricate PW12@NiCo-LDH Acid-Base Bifunctional Catalysts.

Acid-base bifunctional catalysts have attracted increasing attention due to the improved overall efficiency of synthetic reactions. Herein, we reported the successful fabrication of a PW12@NiCo-LDH acid-base bifunctional catalyst by using the in-situ encapsulation-reassembly strategy. The evolution process of morphology and structure was monitored carefully by various time-dependent characterizations. X-ray absorption fine structure (XAFS) and density functional theory (DFT) calculations demonstrated that the terminal oxygen of PW12 in PW12@NiCo-LDH preferred to assemble with the oxygen vacancies on NiCo-LDH. When applied for deacetalization-Knoevenagel condensation, the PW12@NiCo-LDH displayed >99% conversion of benzaldehyde dimethyl acetal (BDMA) and >99% yield of ethyl α-cyanocinnamate (ECC). Moreover, PW12@NiCo-LDH can be recycled at least 10 cycles without obvious structural change, which can be attributed to the confinement of PW12 into the NiCo-LDH nanocage. Such excellent catalytic activity of PW12@NiCo-LDH was benefited from the short mass transfer pathway between acid sites and base sites, which was caused by the stable assembly between PW12 and NiCo-LDH.

Enabling Specific Benzene Oxidation by Tuning the Adsorption Behavior on Au Loaded MgAl Layered Double Hydroxides.

Direct and selective oxidation of benzene to phenol is a long-term goal in industry. Although great efforts have been made in homogenous catalysis, it still remains a huge challenge to drive this reaction via heterogeneous catalysts under mild conditions. Herein, a single-atom Au loaded MgAl-layered double hydroxide (Au1 -MgAl-LDH) with a well-defined structure, in which the Au single atoms are located on the top of Al3+ with Au-O4 coordination as revealed by extended x-ray-absorption fine-structure (EXAFS)and density-functional theory (DFT)calculation is reported. The photocatalytic results prove the Au1 -MgAl-LDH is capable of driving benzene oxidation reaction with O2 in water, and exhibits a high selectivity of 99% for phenol. While contrast experiment shows a ≈99% selectivity for aliphatic acid with Au nanoparticle loaded MgAl-LDH (Au-NP-MgAl-LDH). Detailed characterizations confirm that the origin of the selectivity difference can be attributed to the profound adsorption behavior of substrate benzene with Au single atoms and nanoparticles. For Au1 -MgAl-LDH, single Au-C bond is formed in benzene activation and result in the production of phenol. While for Au-NP-MgAl-LDH, multiple AuC bonds are generated in benzene activation, leading to the crack of CC bond.

A coumarin-pyrazole-based probe for the fluorescence detection of phosgene with high selectivity and sensitivity.

The high toxicity of phosgene poses potential threats to public health and safety. In this work, a novel fluorescent probe was designed to detect phosgene using hydroxyl and pyrazole moieties as the recognition sites. The response to phosgene with probe 1 was fast (less than 30 s), highly selective and sensitive with the limit of detection being 4.78 nM in solution. Furthermore, probe 1 was employed to conveniently fabricate paper test strips for efficiently detecting phosgene gas. The limit of detection was obtained as 0.014 ppm by using a smartphone RGB app, revealing that probe 1 has good prospects for sensitively detecting phosgene gas.

Insight into the Mechanism of Cd2+ Removal by MgAl Layered Double Hydroxides with Different Host-Guest Interactions.

Layered double hydroxides (LDHs) have shown great potential as adsorbents for the removal of heavy metals. Nevertheless, how the host-guest interactions of LDHs affect the removal mechanism remains to be less explored. Herein, CO3 2- /NO3 - /SO4 2- /Cl- intercalated MgAl-LDHs with different host-guest interactions were fabricated and their removal mechanism for Cd2+ was investigated. The removal capacity increased in the order of MgAl-CO3 (127.3 mg/g)

Passivating Oxygen Evolution Activity of NiFe-LDH through Heterostructure Engineering to Realize High-Efficiency Electrocatalytic Formate and Hydrogen Co-Production.

An electrocatalytic methanol oxidation reaction (MOR) is proposed to replace oxygen evolution reaction (OER) in water electrolysis owing to the favorable thermodynamics of MOR than OER. However, there is still a competition between the MOR and the OER when the applied potential is in the conventional OER zone. How to inhibit OER while maintaining efficient MOR is an open and challenging question, and there are few reports focusing on this thus far. Herein, by taking NiFe layered double hydroxide (LDH) as a model catalyst due to its intrinsically high catalytic activity for the OER, the perspective of inhibiting OER is shown and thus promoting MOR through a heterogenous engineering of NiFe-LDH. The engineered heterostructure comprising NiFe-LDH and in situ formed NiFe-hexylaminobenzene (NiFe-HAB) coordination polymer exhibits outstanding electrocatalytic capability for methanol oxidation to formic acid (e.g., the Faradaic efficiencies (FEs) of formate product are close to 100% at various current densities, all of which are much larger than those (53-65%) on unmodified NiFe-LDH). Mechanism studies unlock the modification of NiFe-HAB passivates the OER activity of NiFe-LDH through tailoring the free energies for element reaction steps of the OER and increasing the free energy of the rate-determining step, consequently leading to efficient MOR.

Untangling TMS-EEG responses caused by TMS versus sensory input using optimized sham control and GABAergic challenge.

The combination of transcranial magnetic stimulation (TMS) and electroencephalography (EEG) elegantly probes the excitability and connectivity of the human brain. However, TMS-EEG signals inevitably also contain sensory-evoked responses caused by TMS-associated auditory and somatosensory inputs, constituting a substantial confounding factor. Here we applied our recently established optimized SHAM protocol (Gordon et al., Neuroimage 2021:118708) to disentangle TMS-EEG responses caused by TMS vs. sensory input. One unresolved question is whether these responses superimpose without relevant interaction, a requirement for their disaggregation by the optimized SHAM approach. We applied in 20 healthy subjects a pharmacological intervention using a single oral dose of 20 mg of diazepam, a positive modulator of GABAA receptors. Diazepam decreased the amplitudes of the P60 and P150 components specifically in the ACTIVE TMS and/or the ACTIVE TMS minus SHAM conditions but not in the SHAM condition, pointing to a response caused by TMS. In contrast, diazepam suppressed the amplitude of the N100 component indiscriminately in the ACTIVE TMS and SHAM conditions but not in the ACTIVE TMS minus SHAM condition, pointing to a response caused by sensory input. Moreover, diazepam suppressed the beta-band response observed in the motor cortex specifically after ACTIVE TMS and ACTIVE TMS minus SHAM. These findings demonstrate a lack of interaction of TMS-EEG responses caused by TMS vs. sensory input and validate optimized SHAM-controlled TMS-EEG as an appropriate approach to untangle these TMS-EEG responses. This knowledge will enable the proficient use of TMS-EEG to probe the physiology of the human cortex. KEY POINTS: Optimized SHAM disentangles TMS-EEG responses caused by TMS vs. sensory input. Diazepam differentially modulates TMS-EEG responses caused by TMS vs. sensory input. Diazepam modulation of P60 and P150 indicate TMS-EEG responses caused by TMS. Diazepam modulation of N100 indicate a TMS-EEG response caused by sensory input.