Study on synergistic leaching of potassium and phosphorus from potassium feldspar and solid waste phosphogypsum via coupling reactions

To achieve the resource utilization of solid waste phosphogypsum(PG)and tackle the problem of utilizing potassium feldspar(PF),a coupled synergistic process between PG and PF is proposed in this paper.The study investigates the features of P and F in PG,and explores the decomposition of PF using hydrofluoric acid(HF)in the sulfuric acid system for K leaching and leaching of P and F in PG.The impact factors such as sulfuric acid concentration,reaction temperature,reaction time,material ratio(PG/PF),liquid–solid ratio,PF particle size,and PF calcination temperature on the leaching of P and K is systematically investigated in this paper.The results show that under optimal conditions,the leaching rate of K and P reach more than 93%and 96%,respectively.Kinetics study using shrinking core model(SCM)indicates two significant stages with internal diffusion predominantly controlling the leaching of K.The apparent activation energies of these two stages are 11.92 kJ·mol^(-1)and 11.55 kJ·mol^(-1),respectively.

Metal-organic-framework-derived copper-based catalyst for multicomponent C-S coupling reaction

Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.

Boosting Oxygen Evolution Reaction Performance on NiFe‑Based Catalysts Through d‑Orbital Hybridization

Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.

Defects‑Rich Heterostructures Trigger Strong Polarization Coupling in Sulfides/Carbon Composites with Robust Electromagnetic Wave Absorption

Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,however,constrain their delicate constructions.Herein,an innovative alternative is proposed:carrageenan-assistant cations-regulated(CACR)strategy,which induces a series of sulfides nanoparticles rooted in situ on the surface of carbon matrix.This unique configuration originates from strategic vacancy formation energy of sulfides and strong sulfides-carbon support interaction,benefiting the delicate construction of defects-rich heterostructures in M_(x)S_(y)/carbon composites(M-CAs).Impressively,these generated sulfur vacancies are firstly found to strengthen electron accumulation/consumption ability at heterointerfaces and,simultaneously,induct local asymmetry of electronic structure to evoke large dipole moment,ultimately leading to polarization coupling,i.e.,defect-type interfacial polarization.Such“Janus effect”(Janus effect means versatility,as in the Greek two-headed Janus)of interfacial sulfur vacancies is intuitively confirmed by both theoretical and experimental investigations for the first time.Consequently,the sulfur vacancies-rich heterostructured Co/Ni-CAs displays broad absorption bandwidth of 6.76 GHz at only 1.8 mm,compared to sulfur vacancies-free CAs without any dielectric response.Harnessing defects-rich heterostructures,this one-pot CACR strategy may steer the design and development of advanced nanomaterials,boosting functionality across diverse application domains beyond electromagnetic response.

Highly mass activity electrocatalysts with ultralow Pt loading on carbon black for hydrogen evolution reaction

Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.

Efficient chemical mechanical polishing of W promoted by Fenton-like reaction between Cu^(2+)and H_(2)O_(2)

The Fenton-like reaction between Cu^(2+)and H_(2)O_(2)was employed in chemical mechanical polishing to achieve efficient and high-quality processing of tungsten.The microstructure evolution and material removal rate of tungsten during polishing process were investigated via scanning electron microscopy,X-ray photoelectron spectroscopy,ultraviolet−visible spectrophotometry,and electrochemical experiments.The passivation behavior and material removal mechanism were discussed.Results show that the use of mixed H_(2)O_(2)+Cu(NO_(3))_(2)oxidant can achieve higher polishing efficiency and surface quality compared with the single oxidant Cu(NO_(3))_(2)or H_(2)O_(2).The increase in material removal rate is attributed to the rapid oxidation of W into WO_(3)via the chemical reaction between the substrate and hydroxyl radicals produced by the Fenton-like reaction.In addition,material removal rate and static etch rate exhibit significantly different dependencies on the concentration of Cu(NO_(3))_(2),while the superior oxidant for achieving the balance between polishing efficiency and surface quality is 0.5 wt.%H_(2)O_(2)+1.0 wt.%Cu(NO_(3))_(2).

De novo-design of highly exposed Co−N−C single-atom catalyst for oxygen reduction reaction

The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.

Study on the Fluid-Solid Coupling Seepage of the Deep Tight Reservoir Based on 3D Digital Core Modeling

Deep tight reservoirs exhibit complex stress and seepage fields due to varying pore structures,thus the seepage characteristics are significant for enhancing oil production.This study conducted triaxial compression and permeability tests to investigate the mechanical and seepage properties of tight sandstone.A digital core of tight sandstone was built using Computed Tomography(CT)scanning,which was divided into matrix and pore phases by a pore equivalent diameter threshold.A fluid-solid coupling model was established to investigate the seepage characteristics at micro-scale.The results showed that increasing the confining pressure decreased porosity,permeability,and flow velocity,with the pore phase becoming the dominant seepage channel.Cracks and large pores closed first under increasing pressure,resulted in a steep drop in permeability.However,permeability slightly decreased under high confining pressure,which followed a first-order exponential function.Flow velocity increased with seepage pressure.And the damage mainly occurred in stress-concentration regions under low seepage pressure.Seepage behavior followed linear Darcy flow,the damage emerged at seepage entrances under high pressure,which decreased rock elastic modulus and significantly increased permeability.

Optimized reinforcement of granite residual soil using a cement and alkaline solution: A coupling effect

Granite residual soil (GRS) is a type of weathering soil that can decompose upon contact with water, potentially causing geological hazards. In this study, cement, an alkaline solution, and glass fiber were used to reinforce GRS. The effects of cement content and SiO_(2)/Na2O ratio of the alkaline solution on the static and dynamic strengths of GRS were discussed. Microscopically, the reinforcement mechanism and coupling effect were examined using X-ray diffraction (XRD), micro-computed tomography (micro-CT), and scanning electron microscopy (SEM). The results indicated that the addition of 2% cement and an alkaline solution with an SiO_(2)/Na2O ratio of 0.5 led to the densest matrix, lowest porosity, and highest static compressive strength, which was 4994 kPa with a dynamic impact resistance of 75.4 kN after adding glass fiber. The compressive strength and dynamic impact resistance were a result of the coupling effect of cement hydration, a pozzolanic reaction of clay minerals in the GRS, and the alkali activation of clay minerals. Excessive cement addition or an excessively high SiO_(2)/Na2O ratio in the alkaline solution can have negative effects, such as the destruction of C-(A)-S-H gels by the alkaline solution and hindering the production of N-A-S-H gels. This can result in damage to the matrix of reinforced GRS, leading to a decrease in both static and dynamic strengths. This study suggests that further research is required to gain a more precise understanding of the effects of this mixture in terms of reducing our carbon footprint and optimizing its properties. The findings indicate that cement and alkaline solution are appropriate for GRS and that the reinforced GRS can be used for high-strength foundation and embankment construction. The study provides an analysis of strategies for mitigating and managing GRS slope failures, as well as enhancing roadbed performance.

Deformation mechanism and NPR anchor cable truss coupling support in tunnel through fault fracture zone

To address the issue of extensive deformation in the Tabaiyi Tunnel caused by the fault zone,nuclear magnetic resonance(NMR)technology was employed to analyze the physical and mechanical properties of waterabsorbing mudstone.This analysis aimed to understand the mechanism behind the significant deformations.Drawing from the principle of excavation stress compensation,a support scheme featuring NPR anchorcables and an asymmetric truss support system was devised.To validate the scheme,numerical analysis using a combination of the Discrete Element Method(DEM)-Finite Element Method(FEM)was conducted.Additionally,similar material model tests and engineering measurements were carried out.Field experiments were also performed to evaluate the NPR anchor-cable and truss support system,focusing on anchor cable forces,pressures between the truss and surrounding rock,pressures between the initial support and secondary lining,as well as the magnitude of settlement and convergence deformation in the surrounding rock.The results indicate that the waterinduced expansion of clay minerals,resulting from damage caused by fissure water,accelerated the softening of the mudstone's internal structure,leading to significant deformations in the Tabaiyi Tunnel under high tectonic stress.The original support design fell short as the length of the anchor rods was smaller than the expansion depth of the plastic zone.As a result,the initial support structure bore the entire load from the surrounding rock,and a non-coupled deformation contact was observed between the double-arch truss and the surrounding rock.The adoption of NPR asymmetric anchor-cable support effectively restrained the expansion and asymmetric distribution characteristics of the plastic zone.Considering the mechanical degradation caused by water absorption in mudstone,the rigid constraint provided by the truss proved crucial for controlling the stability of the surrounding rock.These research findings hold significant implications for managing large deformations in soft rock tunnels situated within fractured zones under high tectonic stress conditions.

Impact of Climate Change on Crop-cropland Coupling Relationship:A Case Study of the Loess Plateau in China

Climate change brings new challenges to the sustainable development of agriculture in the new era.Accurately grasping the patterns of climate change impacts on agricultural systems is crucial for ensuring agricultural sustainability and food security.Taking the Loess Plateau(LP),China as an example,this study used a coupling coordination degree model and spatial autocorrelation analysis to portray the spatial and temporal features of crop-cropland coupling relationship from 2000 to 2020 and explored the impact law of climate change through geographically and temporally weighted regression(GTWR).The results were as follows:1)the crop-cropland coupling coordination degree of the LP showed a gradual upward trend from 2000 to 2020,forming a spatial pattern with lower values in the central region and higher values in the surrounding areas.2)There was a positive correlation in the spatial distribution of cropcropland coupling coordination degree in the LP from 2000 to 2020,and the high value-low value(H-L)and low value-low value(L-L)agglomerations continued to expand eastward,while the spatial and temporal evolution of the high value-high value(H-H)and low value-high value(L-H)agglomerations was not obvious.3)The impacts of climatic elements on crop-cropland coupling coordination degree in the LP showed strong heterogeneity in time scales.The inhibitory impacts of summer days(SU)and frost days(FD)accounted for a higher proportion,while the annual average temperature(TEM)had both promoting and inhibiting impacts.The impacts proportion and intensity of extreme heavy precipitation day(R25),continuous drought days(CDD),and annual precipitation(PRE)all experienced significant changes.4)In space,the impacts of SU and FD on the crop-cropland coupling coordination degree varied with latitude and altitude.The adaptability of the LP to R25 gradually strengthened,and the extensions of CDD and increase of PRE led to the increasing inhibition beyond the eastern region of LP,and TEM showed a promoting impact in the Fenwei Plain.As an important grainproducing area in China,the LP should actively deal with the impacts of climate change on the crop-cropland coupling relationship,vigorously safeguard food security,and promote sustainable agricultural development.

Theoretical and Experimental Study on Reaction Coupling: Dehydrogenation of Ethylbenzene in the Presence of Carbon Dioxide

Dehydrogenation of ethylbenzene （EB） to styrene （ST） in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift （RWGS）, was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process. The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3. Coke deposition and deep reduction of active components are the major causes of catalyst deactivation. CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.

Pyroelectricity effect on photoactivating palladium nanoparticles in PbTiO3 for Suzuki coupling reaction

Combining microwave radiation with photocatalytic systems is a promising method to inhibit photogenerated electron-hole recombination and enhance the photocatalytic reaction performance. In this study, we have designed Pd/Pb TiO3 catalysts that can use both microwave fields and photocatalysis. Benefiting from the synergistic effect of microwave field and UV light, the Pb TiO3 crystals convert thermal energy into electrical energy via the pyroelectricity effect, generating positive and negative charges(q+ and q-), while Pd nanoparticles significantly improve the quantum efficiency of the photocatalytic process. The composite catalyst significantly enhances the reaction rate and selectivity of the model Suzuki coupling reaction performed with bromobenzene. Microwave fields can directly act on chemical systems, promoting or changing various chemical reactions in unique ways.

Rapid synthesis of Pd single‐atom/cluster as highly active catalysts for Suzuki coupling reactions

Palladium(Pd)‐based catalysts are essential to drive high‐performance Suzuki coupling reactions,which are powerful tools for the synthesis of functional organic compounds.Herein,we developed a solution‐rapid‐annealing process to stabilize nitrogen‐mesoporous carbon supported Pd single‐atom/cluster(Pd/NMC)material,which provided a catalyst with superior performance for Suzuki coupling reactions.In comparison with commercial palladium/carbon(Pd/C)catalysts,the Pd/NMC catalyst exhibited significantly boosted activity(100%selectivity and 95%yield)and excellent stability(almost no decay in activity after 10 reuse cycles)for the Suzuki coupling reactions of chlorobenzenes,together with superior yield and excellent selectivity in the fields of the board scope of the reactants.Moreover,our newly developed rapid annealing process of precursor solutions is applied as a generalized method to stabilize metal clusters(e.g.Pd,Pt,Ru),opening new possibilities in the construction of efficient highly dispersed metal atom and sub‐nanometer cluster catalysts with high performance.

Cu(I)/Diamine-catalyzed Aryl-alkyne Coupling Reactions

CuI/ethylene diamine/K2CO3/dioxane is shown to be a useful system for the cross coupling reactions of various aryl iodides and bromides with aryl and alkyl alkynes. Compared to the conventional Sonogashira reactions, the new procedure is free of palladium and phosphines.

The Application of Suzuki Coupling Reaction on the Preparation of Carbosilane Dendrimers with 4-(Naphthalen-1-yl)phenyl Core

Carbosilane dendrimers with p-bromophenyl core were synthesized by alternating Grignard and hydrosilylation reaction. And the α-naphthalenyl was connected to the core by the Suzuki coupling reaction. A new carbosilane dendrimer with big π-conjugated structure [4-（naphthalen-l-yl）phenyl core] was given. It shows Suzuki coupling reaction is an effective and powerful core-functionalization method and the satisfactory result can be obtained through prolonging the reaction time with the increase of the generation of dendrimer.

Recent advances in paired electrolysis coupling CO_(2) reduction with alternative oxidation reactions

Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)holds great promise in green energy conversion and storage.However,for current CO_(2) electrolyzers that rely on the oxygen evolution reaction,a large portion of the input energy is"wasted"at the anode due to the high overpotential requirement and the recovery of low-value oxygen.To make efficient use of the electricity during electrolysis,coupling CO_(2)RR with anodic alternatives that have low energy demands and/or profitable returns with high-value products is then promising.Herein,we review the latest advances in paired systems for simultaneous CO_(2) reduction and anode valorization.We start with the cases integrating CO_(2)RR with concurrent alternative oxidation,such as inorganic oxidation using chloride,sulfide,ammonia and urea,and organic oxidation using alcohols,aldehydes and primary amines.The paired systems that couple CO_(2)RR with on-site oxidative upgrading of CO_(2)-reduced chemicals are also introduced.The coupling mechanism,electrochemical performance and economic viability of these co-electrolysis systems are discussed.Thereby,we then point out the mismatch issues between the cathodic and anodic reactions regrading catalyst ability,electrolyte solution and reactant supply that will challenge the applications of these paired electrolysis systems.Opportunities to address these issues are further proposed,providing some guidance for future research.

Sm/TiCl_4 (cat.) system-mediated intermolecular and intramolecular reductive coupling reactions of ketones with esters

Sm/TiCl4 system could well integrate the high reactivity of samarium（Ⅱ） and high deoxygenation capacity of low valent titanium within one system. In this paper, the intermolecular and intramolecular reductive coupling reactions of ketones with esters mediated by metallic samarium （Sm） and a catalytic amount of titanium tetrachloride （TiCl4） were successfully developed. A series of substituted ketones and cyclic β-keto-esters were prepared in moderate to good yields under reflux and neutral conditions.

An Efficient System TiCl_4-Al for the Homocoupling Reaction of Aromatic Aldehydes

The reduction of TiCl4(THF)2 with Al in CH2Cl2 gave a green solution of [Ti2(μ-Cl)2Cl4· (THF)4] (1) which was found to promote the reductive homocoupling of aromatic aldehydes to yield symmetrical 1, 2-diols with high diasterepselectivities.

Ligand assisted copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines

Three types of ligands have been developed for copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines in aqueous solution. Ligands with large steric hindrance and strong electron-donating capacity were beneficial to the reaction. UV–Vis and CV analyses demonstrated that these ligands had strong coordination with copper(I), implying the effect of ligand coordination ability on the stability and catalytic activity of catalytic system.