Metal Ratio Research Articles

Highly-sensitive detection of CP-type synthetic cannabinoids from e-cigarettes by anovel Zn/Bi bimetallic organic framework-derived ZnO-Bi2O3 heterojunctions sensing platform.

Synthetic cannabinoids (SCs), often masqueraded in "e-cigarettes," are novel popular psychoactive substances with diverse structures and complex material compositions, making their detection more challenging for prompt intervention. Herein, a novel electrochemical sensing platform based on Zn/Bi bimetallic organic framework-derived ZnO-Bi2O3 heterojunctions was constructed for the detection of cyclohexanylphenol synthetic cannabinoids (CP-type SCs: CP47,497 and CP55,940). The sensing characteristics of ZnO-Bi2O3 were studied under various conditions, including solvent composition, molar ratio of metal, and calcination temperature. The optimized ZnO-Bi2O3 heterojunction exhibited a larger surface area, more active sites, and stronger stability, conducive to enhanced electrochemical catalytic performance. Under optimal conditions, aZnO-Bi2O3 modified screen-printed electrode (ZnO-Bi2O3/SPE) showed good linear responses toward CP47,497 and CP55,940 within the concentration ranges 7 × 10-9 ~ 5 × 10-6M and 1 × 10-9 ~ 5 × 10-6M, with detection limits of 2.3 × 10-9M and 3.3 × 10-10M, respectively. The sensor also depicted excellent reliability and can be used for on-site electrochemical detection of target objects in e-cigarettes with high recovery. Finally, the electrochemical oxidation mechanisms of CP47,497 and CP55,940 were studied for the first time, and electrochemical fingerprints of CP-type SCs were speculated.

Connecting the liquid fragility to the average weakest metal–oxygen bond of its crystal in oxides

Glass and crystal are inherently different material states in terms of their structural and physical features; consequently, the direct quantitative connection between crystal and glass is lacking. Herein, we first show that the liquid fragility m, which is featured by the negative departure degree of viscosity with the temperature at the glass transition temperature (Tg), has a direct exponential correlation with the ratio of the average longest metal–oxygen and the average phosphorus, silicon, or boron–oxygen bond lengths of the crystal in various oxides including phosphates, silicates, and borates. Such a result can be rationalized by the fact that the fragility m in these glass-formers is associated with the total network rigidity determined by the weakest bond due to the “bucket effect” and the bond pair inheritance of glass from that of the crystal. Our work connects direct features between glass and crystal with identical composition, providing a new viewpoint bridging glass and crystal.

Ni-Co Bimetallic Catalysts Supported on Mixed Oxides (Sc-Ce-Zr) for Enhanced Methane Dry Reforming.

Dry methane reforming (DRM) presents a viable pathway for converting greenhouse gases into useful syngas. Nevertheless, the procedure requires robust and reasonably priced catalysts. This study explored using cost-effective cobalt and nickel combined into a single catalyst with different metal ratios. The reaction was conducted in a fixed reactor at 700 °C. The findings indicate that the incorporation of cobalt significantly enhances catalyst performance by preventing metal sintering, improving metal dispersion, and promoting beneficial metal-support interactions. The best-performing catalyst (3.75Ni+1.25Co-ScCeZr) achieved a good conversion rate of CH4 and CO2 at 46.8 %, and 60 % respectively after 330 minutes while maintaining good stability. The TGA and CO2-TPD analysis results show that the addition of Co to Ni reduces carbon formation, and increases the amount of strong basic sites and isolated O2- species, and the total amount of CO2 desorbed. These results collectively highlight the potential of cobalt-nickel catalysts for practical DRM applications and contribute to developing sustainable energy technologies.

Deoxygenation and isomerization activity balance for NiMo/ZSM-23 catalysts as an effect of Mo/(Ni+Mo) ratio in hydroprocessing of fatty acids

Series of Ni-Mo catalysts based on ZSM-23 zeolite were synthesized by incipient wetness impregnation – with a fixed content of Ni (5 wt. %). These catalysts were tested in a hydroprocessing of a mixture of fatty acids (C16-C18) in a flow reactor at a temperature of 300 °C, a pressure of 2.5 MPa and WHSV = 8.4 h-1. The influence of the ratio of metals on the formation of forms of the active component, as well as on the activity, selectivity to iso-alkanes and the stability of catalysts during the hydroprocessing of a mixture of undiluted fatty acids was determined. The ratio of metals was investigated in the range from 0 to 1. The highest deoxygenation activity and highest isoalkanes yield were found for sample with Mo/(Ni+Mo) ratio equal 0.25, in which, according to the XPS, the Mo/(Ni+Mo) ratio on the surface is 0.4.

Cobalt/iron bimetallic oxide coated with graphitized nitrogen-doped carbon (Fe2O3-CoO@NC) derived from cobalt/iron solid complex as peroxymonosulfate (PMS) activator for efficient bensulfuron-methyl degradation

Cobalt/iron bimetallic oxide coated with graphitized nitrogen-doped carbon (Fe2O3-CoO@NC) was synthesized by convenient solid phase coordination combined with calcination method to activate PMS for the degradation of BSM. A series of Co/Fe bimetallic oxides with different metal ratios were designed and prepared to select the most efficient catalyst and Fe2O3-CoO@NC(Co:Fe = 1:1) demonstrated the highest catalytic activity and the lowest ions leaching. The reasons for high catalytic activity of Fe2O3-CoO@NC(Co:Fe = 1:1) were evaluated by a range of characterization techniques and the results showed it stemmed from higher mental content and larger current density. Complete (100%) degradation of 10 g L−1 BSM was achieved within 10 min under the conditions of 0.05 g L−1 catalyst and 0.3 mmol/L PMS dosage at 25 °C. Moreover, Fe2O3-CoO@NC(Co:Fe = 1:1) showed more excellent catalytic activity and lower ions leaching than Fe2O3, CoO and Fe2O3-CoO, indicating superior bimetallic synergy and carbon encapsulation effect. Furtherly, radical experiments and XPS analysis revealed the main active species and catalytic mechanism of the Fe2O3-CoO@NC/PMS system, respectively. Finally, the degradation pathway of BSM by Fe2O3-CoO@NC/PMS system was deduced by LC-TOF-MS. This paper is aimed to provide a new insight into the convenient preparation method for the construction of catalysts which could reach efficient removal of complex organic pollutants.

Influence of alkali metal formates and calcium formate on workability, hydration and basic properties of reactive powder concrete

AbstractThis work aims to study whether it would be possible to use alkali metal formates and calcium formate in order to increase the workability of reactive powder concrete (RPC) and how these additives affect hydration, mechanical properties and mineralogical composition of RPC. These substances were added together with superplasticizer. Therefore, paper deals with possibility of increase in workability which would be higher when compared to the sole addition of only the superplasticizer themself. The effect of alkali metal formates and their replacement with calcium formate on slump flow, mechanical properties and pH of RPC was studied. Furthermore, the influence of potassium formate and its replacement with calcium formate and with calcium oxide on the hydration of RPC was observed with the help of isothermal calorimetry and thermal analysis. The results showed that the addition of studied compounds allows to achieve an increase in RPC slump flow. However, it is necessary to add these substances in an optimal ratio of alkali metal formate/calcium formate because a higher content of calcium formate leads to a decrease in slump flow. For ideal ratios, the compressive strength after 90 days is still above 218 MPa and the flexural strength is still above 23 MPa. In calorimetric measurements, it was observed that the addition of potassium formate leads to a decrease in the total amount of heat developed in the induction period. According to thermal analysis, additions of the studied additives to RPC caused changes in the content of portlandite and calcite.

A Comprehensive Investigation on Catalytic Behavior of Anaerobic Jar Gassing Systems and Design of an Enhanced Cultivation System.

The rapid and reliable diagnosis of anaerobic bacteria constitutes one of the key procedures in clinical microbiology. Automatic jar gassing systems are commonly used laboratory instruments for this purpose. The most critical factors affecting the cultivation performance of these systems are the level of residual oxygen remaining in the anaerobic jar and the reaction rate determined by the Pd/Al2O3 catalyst. The main objective of the presented study is to design and manufacture an enhanced jar gassing system equipped with an extremum seeking-based estimation algorithm that combines real-time data and a reaction model of the Pd/Al2O3 catalyst. The microkinetic behavior of the palladium catalyst was modeled through a learning-from-experiment methodology. The majority of microkinetic model parameters were derived from material characterization analysis. A comparative validation test of the designed cultivation system was conducted using conventional gas pouches via six different bacterial strains. The results demonstrated high cell viability, with colony counts ranging from 1.26 × 105 to 2.17 × 105 CFU mL-1. The favorable catalyst facets for water formation on Pd surfaces and the crystal structure of Pd/Al2O3 pellets were identified by X-Ray diffraction analysis (XRD). The doping ratio of the noble metal (Pd) and the support material (Al2O3) was validated via energy-dispersive spectroscopy (EDS) measurements as 0.68% and 99.32%, respectively. The porous structure of the catalyst was also analyzed by scanning electron microscopy (SEM). During the reference clinical trial, the estimation algorithm was terminated after 878 iterations, having reached its predetermined termination value. The measured and modelled reaction rates were found to converge with a root-mean-squared error (RMSE) of less than 10-4, and the Arrhenius parameters of ongoing catalytic reaction were obtained. Additionally, our research offers a comprehensive analysis of anaerobic jar gassing systems from an engineering perspective, providing novel insights that are absent from the existing literature.

Ni- and Co-Based MOF-Derived NixCo3-xO4 Materials: As an Efficient Anode for Direct Methanol Fuel Cell Application.

Finding inexpensive and efficient anode materials is crucial for the oxidation of methanol in the direct methanol fuel cell (DMFC), which is the key electrode reaction. Herein, we report metal-organic framework (MOF)-derived Co3O4, NiO, and NixCo3-xO4 (where x = 1.5, 1, and 0.6) materials deposited on nickel foam as efficient anode material for methanol oxidation. Among them, NiCo2O4 exhibited the highest methanol oxidation activity, owing to its lowest charge-transfer resistance (0.097 Ω) and high electrochemically active surface area (1950 cm2), resulting in the lowest onset potential of 0.35 V vs Hg/HgO. The optimized Ni-to-Co ratio and synergistic effect between Ni and Co metals enable NiCo2O4 to achieve the highest mass activity of 151 mA mg-1 and geometric current density of 288 mA cm-2, demonstrating excellent durability over 14 h at 0.6 V. In addition, to optimize methanol concentration, all the electrocatalysts were tested in a range of methanol concentrations, showing 0.5 M methanol as the optimal concentration. This study focuses on optimizing the metal ratio and methanol concentration to achieve the highest catalytic activity. Additionally, this lays the foundation for developing diverse MOF-derived electrocatalysts and advancing DMFCs.

Temperature Changes in Luminescence of Mixed Complexes of Terbium and Samarium with Organic Ligands Based on 2,2-bipyridyldicarboxamides

Solutions in acetonitrile of three mixed complexes of rare earth elements (terbium and samarium) with organic ligands with various pyridine substituents were studied in this work. The ratios of ligands and metals in the resulting complexes were determined, and the stability constants of samarium complexes were calculated using the spectrophotometric titration method. Measurements of absorption, emission and excitation spectra of luminescence, luminescence kinetics of solutions of mixed complexes of rare earth elements with an excess of metal relative to the ligand were carried out at various temperatures in the range 298–328 K. An increase of luminescence intensity of a samarium ion in complex upon heating has been discovered for the first time. The dependences of the luminescence quantum yield and lifetime of mixed complexes on temperature were obtained. A thermometric parameter — the ratio of the integral luminescence intensities of samarium and terbium ions — was proposed, and the temperature sensitivity coefficient of this parameter was determined for different complexes.

Assessment of bi-metal paleo-redox proxies in the Bakken Formation black shales, Williston Basin, North Dakota, USA

The influence of paleoredox conditions and water-mass restriction on trace metal (TM) accumulation in the lower (LBS) and upper black shales (UBS) of the Devonian–Mississippian (D–M) Bakken Formation was assessed utilizing V/Cr, V/(V + Ni), Ni/Co, U/Th, and enrichment factors (EF) for Mo vs. U. These assessments were compared to previously published estimates based on degree of pyritization (DOPT), sulfur‑iron and C–S–Fe relationships, and sedimentological data. Bi–metal ratios suggest >80 % of samples were deposited under suboxic to anoxic/euxinic conditions, whereas DOPT results suggest >60 % of samples were deposited under dysoxic (0.42–0.75 DOPT) bottom–water conditions. DOPT results are in good agreement with C–S–Fe and total S vs. Fe assessments of paleoredox conditions and sedimentological evidence. Good agreement is also seen between Mo/TOC and Mo EF/U EF that both suggest the Bakken shales were deposited under a relatively unrestricted water mass conditions resulting in consistent renewal of TMs into the basin. With TM resupply outpacing drawdown, the basin could support enhanced primary productivity as well as high concentrations of TMs. Trace metal concentrations for the Bakken Fm. show considerable range for Co (0–10,324 ppm), Mo (0–2018 ppm), Ni (0–1574 ppm), U (0–1604 ppm), and V (0–3194 ppm), and bi–metal ratios for the Bakken Fm. are up to 5× greater than those reported for other D–M black shale formations. Bivariate and principal component analysis indicate Mo, Ni, U, and V accumulation was more closely associated with the organic fraction than with reducing conditions, thus accumulation of organic matter during deposition and generation, migration, and biodegradation of hydrocarbons during diagenesis may have influenced the accumulation and distribution of these TMs. Furthermore, changes in biogeochemical processes during the D–M transition may have fundamentally altered marine chemistry, with the evolution of vascular land plants and enhanced terrestrial weathering leading to an increased influx of nutrients into marine waters resulting in the Annulata, Dasberg, and Hangenberg black shale events. Factors controlling TM accumulation during time of deposition (e.g., TM availability, bottom-water redox conditions, adsorption onto organic matter) and during diagenesis and catagenesis (e.g., alteration and break down of organic matter, movement of fluid hydrocarbons or other basinal fluids) likely contribute to the lack of agreement between redox proxies, and subsequently, the lack of applicability of bi–metal ratios in assessing bottom–water conditions for the Bakken shales. Therefore, it is suggested that these bi-metal redox proxies are not an effective means to describe bottom-water conditions during the deposition of the Bakken shales.

Pollution of Heavy Metals in Topsoil of Remote Mountainous Areas in Western Yunnan-Guizhou Plateau

Heavy metals from anthropogenic emissions have had a negative impact on the ecological environment in remote regions. A total of 69 topsoil samples were collected from 13 remote mountainous areas in the western Yunnan-Guizhou Plateau at altitudes of 2 563-4 037 m, and the concentrations of ten heavy metals in the samples were determined. Enrichment characteristics and pollution sources of heavy metals in topsoil were discussed by referencing the enrichment factor （EF）, positive matrix factorization （PMF）, and Pb isotopes. The results showed that the average concentrations of Al, Fe, Cu, V, and Zn in the topsoil were lower than the soil background values in Yunnan Province； the average concentrations of Ni and Pb were similar to the background values； and the average concentrations of Cd, Cr, and Hg were 1.8-3.6 times higher than the background values. The average EF values of Pb, Cr, and Ni were 3.8, 3.4, and 2.3, respectively, showing moderate enrichment according to the EF classification criteria； the average EF values of Cd and Hg were 15.2 and 10.0, reflecting significant enrichment； and the average EF values of the other metals ranged from 1.1 to 1.9, displaying none-weak enrichment. Combining the comparisons of heavy metal concentrations and ratios in topsoil and bedrock and the EF and PMF results, Al, Fe, V, Cr, Cu, Ni, and Zn in topsoil were considered primarily from detrital sources, and the spatial concentration variations of the metals should have been mainly regulated by the parent material. Cadmium, Hg, and Pb were obviously polluted by anthropogenic emissions, and the main sources were non-ferrous metal smelting and coal combustion. The areas with relatively high Cd, Hg, and Pb pollution were mainly distributed in the Jiaozi snow mountain, Bitahai watershed, Luoji Mountain, and Laojun Mountain areas. Anthropogenic emissions contributed 23.8% of the accumulation of heavy metals in the topsoil.

3D Hierarchical Composites of Hydrotalcite-Coated Carbon Microspheres as Catalysts in Baeyer–Villiger Oxidation Reactions

The use of heterogeneous catalysts is fundamental in the search for sustainable chemical processes. Research on hierarchical materials is a growing field aimed at optimizing the synthesis of catalysts. In this work, layered materials with metals of different cationic ratios and three-dimensional hierarchical structures have been synthesized in a simple and easy way using carbon spheres as support. All materials were characterized with various techniques such as XRF, elemental analysis XRD, FT-IR, SEM, and TEM to study their composition and structure. Finally, these materials were used in the Baeyer–Villiger reaction, which was carried out under optimized conditions. The results showed that the metal ratio was an important factor in the coating process, affecting the catalytic capacity of the materials.

The low-dimensional units modulation of 3D floral Fe/Ni@C towards efficient microwave absorption

Metal-organic frameworks (MOF) derivatives have great potential in microwave absorption (MA) due to their customizable components, topology, and high porosity. However, the correlation between the structural parameters of the low-dimensional units and the MA performance of the 3D MOF derivatives remains unclear. Herein, we prepared a series of floral Fe/Ni@C with different petal sizes and aspect ratios to investigate the effect of low-dimensional structural parameters on the MA properties of 3D MOF derivatives. Specifically, we proposed a competitive coordination strategy. By adjusting the ratio of coordination metals, we successfully obtained floral FeNi-MOF-74 with different petal sizes and aspect ratios. Subsequently, the floral Fe/Ni@C was obtained by thermal-field modulation. It shows that, on the one hand, as the petal size increases, the conductive path is extended and the electron hopping is enhanced, thus facilitating the conductivity loss. And, with the rise of the petal aspect ratio, the tip effect is enhanced, which strengthens the polarization loss. On the other hand, the graphitization degree of the carbon components as well as the size and magnetic properties of the alloy particles can be effectively modulated by optimizing the thermal field modulation temperature. Noteworthily, under the conditions of a coordination metal ratio of 1:1 and an annealing temperature of 700 °C, the obtained MOF derivative exhibited excellent microwave absorption (−65.47 dB at 1.56 mm) and broadband (6.09 GHz at 1.76 mm). This strategy provides new ideas for modulating the microstructure and electromagnetic properties of MOF derivatives.

Effect of processing parameters and carbon to metal ratio on microstructure and mechanical properties of (MoTaTiVW)Cx high entropy carbide produced by reactive spark plasma sintering

(MoTaTiVW)Cx high entropy ceramics with varying carbon to metal ratio in the range of 0.75–0.97 were synthesized by by reactive spark plasma sintering. The effect of ball milling time on particle size, phase evolution and carbon pick-up due to toluene decomposition were studied. Formation of single-phase high entropy carbide having face-centered cubic (FCC) crystal structure was confirmed by X-ray diffraction (XRD), electron backscattered diffraction (EBSD) and Selected area diffraction pattern (SAED) analysis of the sintered compacts. Transmission Kikuchi Diffraction images revealed presence of equiaxed nature of the grains. Transmission electron microscopy images revealed the presence of an intergranular phase at grain boundaries and triple junctions. 3D-Atom Probe Tomography studies showed uniform distribution of elements within the grains with some segregation of impurity elements Fe and Co to the grain boundaries indicating minor contribution of liquid phase sintering to densification. The grain size of single-phase sintered compacts ranged between 1.69 ± 0.60 μm to 4.6 ± 1.0 μm. A low sintering temperature and higher milling time resulted in finer grain size The microhardness was found to increase with milling time and C/M ratio. The microhardness, Young's modulus and indentation fracture toughness lied between 2221 HV0.1 to 2732 HV0.1, 370 GPa–473 GPa, 3.6 MPa m1/2 to 4.4 MPa m1/2, respectively. The highest microhardness and indentation fracture toughness was found to be 2732 ± 80 HV0.1 and 4.4 MPa m1/2 on par with reported literature for other high entropy carbides.

Enhancement of Catalytic Activity via Inevitable Reconstruction of the Ni-Mo Interface for Alkaline Hydrogen Oxidation.

The inevitable oxidation of nickel-metal-based catalysts exposed to the air will lead to instability and poor reproducibility of a catalytic interface, which is usually ignored and greatly hinders their application for the catalysis of alkaline hydrogen oxidation. The details on the formation of a world-class nickel-based HOR catalyst Ni3-MoOx/C-500 are reported via an interfacial reconstruction triggered by passive oxidation upon air exposure. Interfacial reconstruction, initiated with various Ni-Mo metal ratios and annealing temperature, can fine-tune the Ni-Mo interface with an increased work function and a reduced d-band center. The optimized Ni3-MoOx/C exhibits a record high mass activity of 102.8mA mgNi -1, a top-level exchange current density of 76.5µA cmNi -2, and exceptional resistance to CO poisoning at 1000ppm CO for hours. The catalyzed alkaline exchange membrane fuel cell exhibits a maximum power output of 600mW cm-2 and excellent stability, ranking it as one of the most active non-precious metals HOR catalysts to date.

Cloud point Extraction Of Methimazole By Direct (UV- Vis Spectrophotometer) And Indirect (Flame Atomic Absorption) methods

Abstract A new technique based on the formation of a chelate Methimazole-Fe(III) at 400 nm was used for the determination of Methimazole 114 as a surfactant in some pharmaceuticals using indirect flame atomic absorption spectroscopy (FAAS) and UV-visible methods based on Triton turbidity extraction. The optimal turbidity extraction temperature was 75.0°C after 25 min of extraction of the complex [MET-Fe(III)] with ethanol. The structure of the Methimazole-Fe(III) chelate was determined by the molar ratio method. A 1:1 L:M (ligand:metal) ratio was produced. The Beer law was employed in the concentration range of 2.5-30 and 2.5-32.5 g/mL for the UV and FAAS, respectively.. The limits of detection (LOD) and quantification (LOQ) were (0.3784) g/ml and (1.2612) g/ml, respectively, for these techniques. The technique has been approved and successfully used in the production of pharmaceutical preparations such as: B. Methimazole capsules sold in Iraq. The analytical results were validated by statistical and recycling studies with satisfactory results.

Investigation of Copper Anodization Products with Temperature and Chemical Solution Changes

The rapid breakdown anodization (RBA) process was used to modify the copper surface and produce copper oxide powder. The effects of the temperature and inhibitors like glycerol and ethylene glycol were studied. The rate of corrosion increased dramatically at low temperatures, whereas it decreased at high temperatures. Cubic Cu2O particles were formed on the anode. Their volumes increased with increasing temperatures. Scanning electron microscope (SEM) images show the production of semispherical particles in the powder formed at low temperatures, but these particles congregate and combine at high temperatures. After using the glycerol, octahedron and semispherical Cu2O particles were formed on the anode and cathode, respectively. The findings confirm the concept that the anodizing process's temperature may be utilized for controlling the oxide to metal ratio. Significant slowing of the anodic process occurs at high ratios for both inhibitors.

Investigation of Copper Anodization Products with Temperature and Chemical Solution Changes

The rapid breakdown anodization (RBA) process was used to modify the copper surface and produce copper oxide powder. The effects of the temperature and inhibitors like glycerol and ethylene glycol were studied. The rate of corrosion increased dramatically at low temperatures, whereas it decreased at high temperatures. Cubic Cu2O particles were formed on the anode. Their volumes increased with increasing temperatures. Scanning electron microscope (SEM) images show the production of semispherical particles in the powder formed at low temperatures, but these particles congregate and combine at high temperatures. After using the glycerol, octahedron and semispherical Cu2O particles were formed on the anode and cathode, respectively. The findings confirm the concept that the anodizing process's temperature may be utilized for controlling the oxide to metal ratio. Significant slowing of the anodic process occurs at high ratios for both inhibitors.

Enhancing photocatalytic performance of rose-shaped Co/Ni bimetallic organic framework for reducing CO2 to CO under visible light

Co-MOF-74, composed of Co salt as the metal source and 2,5-dihydroxyterephthalic acid as the organic ligand, is widely used as a catalyst for the photocatalytic reduction of CO2 due to its open metal sites, high porosity, large specific surface area, and high CO2 adsorption capacity. However, its effectiveness in CO2 conversion is limited by weak electron transfer capabilities and a high rate of electron/hole pair recombination. To address these limitations, a bimetallic strategy was employed to significantly improve the catalytic performance of Co-MOF-74 for photocatalytic CO2 reduction. Stable bimetallic Co/Ni-MOF-74-x (x = 1, 2, 3) with controllable morphology and metal ratios were synthesized by adjusting the molar ratios of Co2+ and Ni2+ and combining them with 2,5-dihydroxyterephthalic acid. The introduction of Ni2+ led to a significant increase in the specific surface area, from 204.999 m2/g (Co/Ni-MOF-74) to 790.873 m2/g (Co/Ni-MOF-74-1). In addition, the band gap of bimetallic Co/Ni-MOF-74-1 was narrowed to 1.4 eV, which enhanced charge transfer. As a result, photocatalytic experiments demonstrated that the CO2 conversion efficiency of bimetallic Co/Ni-MOF-74-1 was significantly improved, reaching 4.539 mmol/g/h, compared to that of the monometallic Co-MOF-74. Finally, a synergistic photocatalytic mechanism involving ligand activation was proposed to explain the reaction process of the bimetallic Co/Ni-MOF-74 catalyst. Meanwhile, this study highlights that the bimetallic strategy is an effective approach to optimizing the performance of MOF catalysts for the photocatalytic reduction of CO2.

Modulation of p-Block Electron Orbits in Metal-Organic Frameworks for CO2 Capture and Electrochemical Reduction.

Developing catalysts with excellent CO2 capture capability and electrochemical CO2 reduction reaction (CO2RR) at a wide potential range simultaneously is significant but remains a formidable challenge. Here, two novel InMg defective trinuclear cluster-based MOFs (SNNU-41 and SNNU-42) with abundant p-block unsaturated coordinated sites were reported and exhibited good CO2 capture and CO2RR performance simultaneously. Due to the suitable micropores, SNNU-41 showed higher CO2 capture ability at different adsorption pressure conditions. On account of the rigid framework and the closer p band center to Fermi level, SNNU-42 accelerated the conversion of CO2 molecule to C1 efficiency. Notably, via adjusting the ratio of p-block metal (In) in the SNNU-42 framework, the performance of the CO2RR was promoted drastically. SNNU-42 with the InMg (1:1.8) mixed cluster delivered an excellent Faradaic efficiency of 91.3% for C1 products and high selectivity of 72.0% for HCOOH at -2.5 V (vs Ag/Ag+) with a total current density of 77.2 mA cm-2. This work provides a possibility for efficient CO2 capture and CO2RR electrocatalysts through the modulation of electronic structures and composition in MOFs.