High-Entropy Oxide of (BiZrMoWCeLa)O2 as a Novel Catalyst for Vanadium Redox Flow Batteries.

In this study, new fluorite high-entropy oxide (HEO), (BiZrMoWCeLa)O2, nanoparticles were produced using a surfactant-assisted hydrothermal technique followed by calcination and were used as novel catalytic materials for vanadium redox flow batteries (VRFBs). The HEO calcined at 750 °C (HEO-750) demonstrates superior electrocatalytic activity toward V3+/V2+ and VO2+/VO2+ redox couples compared to those of cells assembled with other samples. The charge-discharge tests further confirm that VRFBs using the HEO-750 catalyst demonstrate excellent Coulombic efficiency, voltage efficiency, and energy efficiency of 97.22, 87.47, and 85.04% at a current density of 80 mA cm-2 and 98.10, 74.76, and 73.34% at a higher current density of 160 mA cm-2, respectively. Moreover, with 500 charge-discharge cycles, there is no discernible degradation. These results are attributed to the calcination heat treatment, which induces the formation of a new single-phase fluorite structure, which facilitates the redox reactions of the vanadium redox couples. Furthermore, a high surface area, wettability, and plenty of oxygen vacancies can give more surface electroactive sites, improving the electrochemical performance, the charge transfer of the redox processes, and the stability of the VRFBs' electrode. This is the first report on the development of fluorite structure HEO nanoparticles in VRFBs, and it opens the door to further research into other HEOs.

Surface Electroactive Sites of Tungstated Zirconia Catalysts for Vanadium Redox Flow Batteries.

Surface electroactive sites for tungstate zirconia (WZ) were created by utilizing tungstate-immobilized UiO-66 as precursors via a double-solvent impregnation method under a mild calcination temperature. The WZ-22-650 catalyst, containing a moderate W content (22%), demonstrated a high density of surface electroactive sites. Proper heat treatment facilitated the binding of oligomeric tungsten clusters to stabilized tetragonal ZrO2, resulting in improved catalytic performance toward the VO2+/VO2+ redox couples compared to other tested samples. The substantial surface area, mesoporous structure, and establishment of new W-O-Zr bonds affirm the firm anchoring of WOx to ZrO2. This robust attachment enhances surface electroactive sites, elevating the electrochemical performance of vanadium redox flow batteries (VRFBs). Charge-discharge tests further demonstrate that the superior voltage efficiency (VE) and energy efficiency (EE) for VRFBs using the WZ-22-650 catalyst are 87.76 and 83.94% at 80 mA cm-2, which are 13.42% VE and 10.88% EE better than heat-treated graphite felt, respectively. Even at a higher current density of 160 mA cm-2, VRFBs utilizing the WZ-22-650 catalyst maintained considerable efficiency, recording VE and EE values of 76.76 and 74.86%, respectively. This facile synthesis method resulted in WZ catalysts displaying superior catalytic activity and excellent cyclability, offering a promising avenue for the development of metal-oxide-based catalysts.

Microbial changes and associated metabolic responses modify host plant adaptation in Stephanitis nashi.

Symbiotic microorganisms are essential for the physiological processes of herbivorous pests, including the pear lace bug Stephanitis nashi, which is known for causing extensive damage to garden plants and fruit trees due to its exceptional adaptability to diverse host plants. However, the specific functional effects of the microbiome on the adaptation of S. nashi to its host plants remains unclear. Here, we identified significant microbial changes in S. nashi on 2 different host plants, crabapple and cherry blossom, characterized by the differences in fungal diversity as well as bacterial and fungal community structures, with abundant correlations between bacteria or fungi. Consistent with the microbiome changes, S. nashi that fed on cherry blossom demonstrated decreased metabolites and downregulated key metabolic pathways, such as the arginine and mitogen-activated protein kinase signaling pathway, which were crucial for host plant adaptation. Furthermore, correlation analysis unveiled numerous correlations between differential microorganisms and differential metabolites, which were influenced by the interactions between bacteria or fungi. These differential bacteria, fungi, and associated metabolites may modify the key metabolic pathways in S. nashi, aiding its adaptation to different host plants. These results provide valuable insights into the alteration in microbiome and function of S. nashi adapted to different host plants, contributing to a better understanding of pest invasion and dispersal from a microbial perspective.

On the mechanism of intermolecular nitrogen-atom transfer from a lattice-isolated diruthenium nitride intermediate.

Catalyst confinement within microporous media provides the opportunity to site isolate reactive intermediates, enforce intermolecular functionalization chemistry by co-localizing reactive intermediates and substrates in molecular-scale interstices, and harness non-covalent host-guest interactions to achieve selectivities that are complementary to those accessible in solution. As part of an ongoing program to develop synthetically useful nitrogen-atom transfer (NAT) catalysts, we have demonstrated intermolecular benzylic amination of toluene at a Ru2 nitride intermediate confined within the interstices of a Ru2-based metal-organic framework (MOF), Ru3(btc)2X3 (btc = 1,3,5-benzenetricarboxylate, i.e., Ru-HKUST-1 for X = Cl). Nitride confinement within the extended MOF lattice enabled intermolecular C-H functionalization of benzylic C-H bonds in preference to nitride dimerization, which was encountered with soluble molecular analogues. Detailed study of the kinetic isotope effects (KIEs, i.e., kH/kD) of C-H amination, assayed both as intramolecular effects using partially labeled toluene and as intermolecular effects using a mixture of per-labeled and unlabeled toluene, provided evidence for restricted substrate mobility on the time scale of interstitial NAT. Analysis of these KIEs as a function of material mesoporosity provided approximate experimental values for functionalization in the absence of mass transport barriers. Here, we disclose a combined experimental and computational investigation of the mechanism of NAT from a Ru2 nitride to the C-H bond of toluene. Computed kinetic isotope effects for a H-atom abstraction (HAA)/radical rebound (RR) mechanism are in good agreement with experimental data obtained for C-H amination at the rapid diffusion limit. These results provide the first detailed analysis of the mechanism of intermolecular NAT to a C-H bond, bolster the use of KIEs as a probe of confinement effects on NAT within MOF lattices, and provide mechanistic insights unavailable by experiment because rate-determining mass transport obscured the underlying chemical kinetics.

Development of a Lightweight LTO/Cu Electrode as a Flexible Anode via Etching Process for Lithium-Ion Batteries.

In recent years, flexible energy storage devices have attracted the growing demand for flexible electronic systems. Therefore, research on reliable electrodes with high mechanical flexibility and good electronic and lithium-ion conductivity has become critical. Carbon-coated Li4Ti5O12 (LTO) nanostructures find essential applications in high-performance lithium-ion batteries (LiBs). Nevertheless, the conventional copper current collector with a thickness of several micrometers accounts for a large proportion of the LiB, making the low-energy density LiB with much less flexibility. Here, hundred nm-thick (LTO/Cu) copper foil-LTO nanostructures are fabricated using a scalable and straightforward process which can be assembled into a film into a flexible, lightweight electrode by etching a conventional copper foil to form an ultra-thin copper layer for LIBs (<1 µm). This process provides essential flexibility to the as-prepared electrode and provides template support for simple fabrication. The LiB cell using the novel LTO/Cu as the anode exhibits an energy capacity of 123 mA h/g during 40 charge-discharge cycles at a 0.1C rate. Besides, the coulombic efficiency of the LiB using LTO/Cu remains over 99% after 40 cycles. These results show the uses of this novel anode and its potential in high-density and flexible commercial lithium-ion batteries.

Simple way of making free-standing cathode electrodes for flexible lithium-ion batteries.

The flexible electrodes used in the lithium-ion battery (LIB) offer an excellent opportunity to be bent and folded without deforming their electrochemical characteristics. However, a flexible electrode does not include metal foil as a current collector, limiting the LIB's flexibility and weakening the mechanical strength. This study fabricates flexible LiFePO4 (LFP) free-standing electrodes by a scalable and straightforward solution-based etching process. The obtained free-standing electrodes show capacities and bending performances that are similar to the conventional electrodes with aluminum current collectors. This study opens a new avenue for developing a free-standing electrode for low-cost and flexible lithium-ion batteries.

Mechanochemistry of Group 4 Element-Based Metal-Organic Frameworks.

Mechanochemical synthesis is emerging as an environmentally friendly yet efficient approach to preparing metal-organic frameworks (MOFs). Herein, we report our systematic investigation on the mechanochemical syntheses of Group 4 element-based MOFs. The developed mechanochemistry allows us to synthesize a family of Hf4O4(OH)4(OOC)12-based MOFs. Integrating [Zr6O4(OH)4(OAc)12]2 and [Hf6O4(OH)4(OAc)12]2 under the mechanochemical conditions leads to a unique family of cluster-precise multimetallic MOFs that cannot be accessed by the conventional solvothermal synthesis. Extensive efforts have not yielded an effective pathway for preparing TiIV-derived MOFs, tentatively because of the relatively low Ti-O bond dissociation energy.

Structure, reactivity, and spectroscopy of nitrogenase-related synthetic and biological clusters.

The reduction of dinitrogen (N2) is essential for its incorporation into nucleic acids and amino acids, which are vital to life on earth. Nitrogenases convert atmospheric dinitrogen to two ammonia molecules (NH3) under ambient conditions. The catalytic active sites of these enzymes (known as FeM-cofactor clusters, where M = Mo, V, Fe) are the sites of N2 binding and activation and have been a source of great interest for chemists for decades. In this review, recent studies on nitrogenase-related synthetic molecular complexes and biological clusters are discussed, with a focus on their reactivity and spectroscopic characterization. The molecular models that are discussed span from simple mononuclear iron complexes to multinuclear iron complexes and heterometallic iron complexes. In addition, recent work on the extracted biological cofactors is discussed. An emphasis is placed on how these studies have contributed towards our understanding of the electronic structure and mechanism of nitrogenases.

Miniaturized tri-notched wideband bandpass filter with ultrawide upper stopband suppression.

Stepped impedance resonator (SIR) and its derivative resonators are widely used in the design of microwave filters. However, many spurious modes will be introduced into the stopband, resulting in lower upper stopband suppression and performance degradation. Based on the principle of slit line, a method to enhance the upper stopband suppression is proposed and verified by a miniaturized tri-notched wideband bandpass filter based on stub loaded ring resonator (SLRR) and shorted-stub loaded SIR (SSLSIR). The wideband is formed by coupling SLRR and interdigital lines, which has a rectangular DGS on the back of the substrate. Three notched bands with controllable positions in the passband can be produced by inserting two different SSLSIRs inside and outside the SLRR. Four slit lines are loaded on the low impedance stub of SSLSIR to adjust the high-order modes close to the transmission zeros (TZs). The operating frequency of the filter is 2.2-7.6 GHz, and the three notched bands are located at 2.97 GHz, 5.75 GHz and 6.46 GHz, respectively. The measurement results show that the - 20 dB enhanced upper stopband of the filter can reach 32 GHz, which proves that the filter has the characteristic of ultrawide upper stopband suppression while keeping the miniaturization.

Solar to hydrocarbon production using metal-free water-soluble bulk heterojunction of conducting polymer nanoparticle and graphene oxide.

This work demonstrates the first example of interfacial manipulation in a hybrid photocatalyst based on poly(3-hexylthiophene-2,5-diyl) (P3HT) nanoparticle and graphene oxide (GO) bulk heterojunctions to efficiently reduce CO2 into selective industrial hydrocarbons under gas-phase reaction and visible-light illumination. High selectivity of chemical products (methanol and acetaldehyde) was observed. Moreover, the hybrid photocatalyst's solar-to-fuel conversion efficiency was 13.5 times higher than that of pure GO. The increased production yield stems from the co-catalytic and sensitizing role of P3HT in the hybrid system due to its ability to extend light absorption to the visible range and improve interfacial charge transfer to GO. The hybrid P3HT-GO formed a type II heterojunction, and its static and dynamic exciton behaviors were examined using fluorescence spectroscopy and exciton lifetime mapping. A reduced fluorescence decay time was observed by interfacial manipulation for improved dispersion, indicating a more efficient charge transfer from the excited P3HT to GO. Thus, the conducting polymer nanoparticles, 2D nanocarbon, have demonstrated superior performance as a metal-free, non-toxic, low-cost, and scalable heterogeneous photocatalyst for CO2 reduction to solar fuel, a solid-gas system.

Nanoscale redox mapping at the MoS2-liquid interface.

Layered MoS2 is considered as one of the most promising two-dimensional photocatalytic materials for hydrogen evolution and water splitting; however, the electronic structure at the MoS2-liquid interface is so far insufficiently resolved. Measuring and understanding the band offset at the surfaces of MoS2 are crucial for understanding catalytic reactions and to achieve further improvements in performance. Herein, the heterogeneous charge transfer behavior of MoS2 flakes of various layer numbers and sizes is addressed with high spatial resolution in organic solutions using the ferrocene/ferrocenium (Fc/Fc+) redox pair as a probe in near-field scanning electrochemical microscopy, i.e. in close nm probe-sample proximity. Redox mapping reveals an area and layer dependent reactivity for MoS2 with a detailed insight into the local processes as band offset and confinement of the faradaic current obtained. In combination with additional characterization methods, we deduce a band alignment occurring at the liquid-solid interface.

In Crystallo Snapshots of Rh2-Catalyzed C-H Amination.

While X-ray crystallography routinely provides structural characterization of kinetically stable pre-catalysts and intermediates, elucidation of the structures of transient reactive intermediates, which are intimately engaged in bond-breaking and -making during catalysis, is generally not possible. Here, we demonstrate in crystallo synthesis of Rh2 nitrenoids that participate in catalytic C-H amination, and we characterize these transient intermediates as triplet adducts of Rh2. Further, we observe the impact of coordinating substrate, which is present in excess during catalysis, on the structure of transient Rh2 nitrenoids. By providing structural characterization of authentic C-H functionalization intermediates, and not kinetically stabilized model complexes, these experiments provide the opportunity to define critical structure-activity relationships.

Probing the active site in single-atom oxygen reduction catalysts via operando X-ray and electrochemical spectroscopy.

Nonnoble metal catalysts are low-cost alternatives to Pt for the oxygen reduction reactions (ORRs), which have been studied for various applications in electrocatalytic systems. Among them, transition metal complexes, characterized by a redox-active single-metal-atom with biomimetic ligands, such as pyrolyzed cobalt-nitrogen-carbon (Co-Nx/C), have attracted considerable attention. Therefore, we reported the ORR mechanism of pyrolyzed Vitamin B12 using operando X-ray absorption spectroscopy coupled with electrochemical impedance spectroscopy, which enables operando monitoring of the oxygen binding site on the metal center. Our results revealed the preferential adsorption of oxygen at the Co2+ center, with end-on coordination forming a Co2+-oxo species. Furthermore, the charge transfer mechanism between the catalyst and reactant enables further Co-O species formation. These experimental findings, corroborated with first-principle calculations, provide insight into metal active-site geometry and structural evolution during ORR, which could be used for developing material design strategies for high-performance electrocatalysts for fuel cell applications.

Redox Communication between Two Diarylamido/Bis(phosphine) (PNP)M Moieties Bridged by Ynediyl Linkers (M = Ni, Pd, Pt).

A series of binuclear homo- and heterobimetallic complexes of the general type (PNP)M-[linker]-M(PNP) have been prepared (M = Ni, Pd, Pt; PNP = a diarylamido/bis(phosphine) pincer ligand; -[linker]- = -C≡C-, -C≡CC≡C-, -C≡CC6H4C≡C-). Each (PNP)M site can be oxidized by one electron, and this work reports the investigation of the mixed-valence behavior in terms of the communication between the two redox sites and the degree of the delocalization in the monooxidized cation. The compounds were evaluated using cyclic voltammetry, UV-vis-NIR and EPR spectroscopy, X-ray crystallography, and DFT calculations. The complex with the longest examined linker, (PNP)Ni-C≡CC6H4C≡C-Ni(PNP) (9Ni), exhibited no discernible communication between the redox sites. The homobimetallic complexes (PNP)M-C≡CC≡C-M(PNP) (6M) displayed a lower degree of communication in comparison to the -C≡C- linker analogues (PNP)M-C≡C-M(PNP) (3M). Within each of these two subsets, the relative degree of communication and delocalization was determined to be Pd < Ni ≤ Pt. On the Robin-Day scale, compounds 6M can be assigned class I for M = Pd and class II for M = Ni, Pt. Complex 3Pd also falls into class II, while 3Ni and 3Pt may be viewed as borderline class II/III cases. It is likely that the communication in the Ni systems has the advantage of the smaller size of Ni, resulting in a greater physical proximity of the redox sites, while the 5d metal Pt possesses the greatest ability for orbital interaction with the -C≡C- linker.

Atomically Precise Crystalline Materials Based on Kinetically Inert Metal Ions via Reticular Mechanopolymerization.

Atomistic control of the coordination environment of lattice ions and the distribution of metal sites within crystalline mixed-metal coordination polymers remain significant synthetic challenges. Herein is reported the mechanochemical synthesis of a reticular family of crystalline heterobimetallic metal-organic frameworks (MOFs) is now achieved by polymerization of molecular Ru2 [II,III] complexes, featuring unprotected carboxylic acid substituents, with Cu(OAc)2 . The resulting crystalline heterobimetallic MOFs are solid solutions of Ru2 and Cu2 sites housed within [M3 L2 ] phases. The developed mechanochemical strategy is modular and allows for systematic control of the primary coordination sphere of the Ru2 sites within an isoreticular family of materials. This strategy is anticipated to provide a rational approach to atomically precise mixed-metal materials.

Microwave-assisted pyrolysis of Pachira aquatica leaves as a catalyst for the oxygen reduction reaction.

In this study, biomimetic Mg-N x -C y from Pachira aquatica leaves were mixed with carbon black (L/C catalyst), in which the mixture was treated by a conventional microwave oven at 700 W and 2 min, exhibiting high catalytic activity for the oxygen reduction reaction (ORR). By using a microwave-assisted process, it not only offers a cheaper and faster way to synthesize the catalyst compared to the conventional furnace process but also avoids the decomposition of the N4-structure. Using the optimized conditions, the L/C catalyst exhibits an electron transfer number of 3.90 and an HO2 - yield of only 5% at 0.25 V vs. RHE, which is close to the perfect four electron-transfer pathway. Besides, the L/C catalyst offers superior performance and long-term stability up to 20 000 s. The L/C catalyst contains a high proportion of quaternary-type nitrogen, Mg-N x -C y , and -C-S-C- which can be the active sites for the ORR.

Measuring and Modulating Substrate Confinement during Nitrogen-Atom Transfer in a Ru2-Based Metal-Organic Framework.

The porosity and synthetic tunability of metal-organic frameworks (MOFs) has motivated interest in application of these materials as designer heterogeneous catalysts. While understanding substrate mobility in these materials is critical to the rational development of highly active catalyst platforms, experimental data are rarely available. Here we demonstrate kinetic isotope effect (KIE) analysis enables direct evaluation of the extent of substrate confinement as a function of material mesoporosity. Further, we provide evidence that suggests substrate confinement within a microporous Ru2-based MOF gives rise to quantum tunneling during interstitial C-H amination. The reported data provide the first evidence for tunneling during interstitial MOF chemistry and illustrate an experimental strategy to evaluate the impact of material structure on substrate mobility in porous catalysts.

Templating metastable Pd2 carboxylate aggregates.

Evaluation of the potential for metal-metal (M-M) cooperation to enable catalysis requires access to specific polynuclear aggregates that display appropriate geometry and size. In many cases, exerting synthetic control over the aggregation of simple metal salts is a challenge. For example, Pd(ii) acetate self assembles as a trimer (i.e. Pd3(OAc)6) both in the solid state and in solution and does not feature close Pd-Pd interactions. Related carboxylate-supported Pd2 aggregates (i.e. Pd2(OAc)4), which would feature close Pd-Pd interactions, are thermodynamically metastable in solution phase and thus largely unavailable. Here we demonstrate ion metathesis within pre-formed metal-organic frameworks (MOFs) to prepare metastable Pd2 tetracarboxylates sites. The newly synthesized materials are characterized by elemental analysis, PXRD, SCXRD, EXAFS, XANES, and gas adsorption analysis. In addition, the critical role of network solvation on the kinetics of ion metathesis was revealed by coupled TGA-MS and ICP-MS experiments. The demonstration of templated ion metathesis to generate specific metastable coordination sites that are inaccessible in solution phase chemistry represents a new opportunity to interrogate the chemistry of specific polynuclear metal aggregates.

Application of interface material and effects of oxygen gradient on the performance of single-chamber sediment microbial fuel cells (SSMFCs).

Single-chamber sediment microbial fuel cells (SSMFCs) have received considerable attention nowadays because of their unique dual-functionality of power generation and enhancement of wastewater treatment performance. Thus, scaling up or upgrading SSMFCs for enhanced and efficient performance is a highly crucial task. Therefore, in order to achieve this goal, an innovative physical technique of using interface layers with four different pore sizes embedded in the middle of SSMFCs was utilized in this study. Experimental results showed that the performance of SSMFCs employing an interface layer was improved regardless of the pore size of the interface material, compared to those without such layers. The use of an interface layer resulted in a positive and significant effect on the performance of SSMFCs because of the effective prevention of oxygen diffusion from the cathode to the anode. Nevertheless, when a smaller pore size interface was utilized, better power performance and COD degradation were observed. A maximum power density of 0.032mW/m2 and COD degradation of 47.3% were obtained in the case of an interface pore size of 0.28µm. The findings in this study are of significance to promote the future practical application of SSMFCs in wastewater treatment plants.

In Operando Analysis of Diffusion in Porous Metal-Organic Framework Catalysts.

The potential to exert atomistic control over the structure of site-isolated catalyst sites, as well as the topology and chemical environment of interstitial pore spaces, has inspired efforts to apply porous metal-organic frameworks (MOFs) as catalysts for fine chemical synthesis. In analogy to enzyme-catalyzed reactions, MOF catalysts have been proposed as platforms in which substrate confinement could be used to achieve chemo- and stereoselectivities that are orthogonal to solution-phase catalysts. In order to leverage the tunable pore topology of MOFs to impact catalyst selectivity, catalysis must proceed at interstitial catalyst sites, rather than at solvent-exposed interfacial sites. This Minireview addresses challenges inherent to interstitial MOF catalysis by 1) describing the diffusional processes available to sorbates in porous materials, 2) discussing critical factors that impact the diffusion rate of substrates in porous materials, and 3) presenting in operando experimental strategies to assess the relative rates of substrate diffusion and catalyst turnover in MOF catalysis. It is anticipated that the continued development of in operando tools to evaluate substrate diffusion in porous catalysts will advance the application of these materials in fine chemical synthesis.