Waste acid recovery utilizing monovalent cation permselective membranes through selective electrodialysis

Selective electrodialysis(SED)has surfaced as a highly promising membrane separation technique in the realm of acid recovery owing to its ability to effectively separate monovalent ions through the utilization of a potential difference.However,the current SED process is limited by conventional commercial monovalent cation permselective membranes(MCPMs).This study systematically investigates the use of an independently developed MCPM in the SED process for acid recovery.Various factors such as current density,volume ratio,initial ion concentration,and waste acid systems are considered.The independently developed MCPM offers several advantages over the commercial monovalent selective cation-exchange membrane(CIMS),including higher recovered acid concentration,better ion flux ratio,improved acid recovery efficiency,increased recovered acid purity,and higher current efficiency.The SED process with the MCPM achieves a recovered acid of 95.9%and a concentration of 2.3 mol·L^(–1) in the HCl/FeCl_(2) system,when a current density of 20 mA·cm^(-2) and a volume ratio of 1:2 are applied.Similarly,in the H_(2)SO_(4)/FeSO_(4) system,a purity of over 99%and a concentration of 2.1 mol·L^(–1) can be achieved in the recovered acid.This study thoroughly examines the impact of operation conditions on acid recovery performance in the SED process.The independently developed MCPM demonstrates outstanding acid recovery performance,highlighting its potential for future commercial utilization.

Recent developments in selective laser processes for wearable devices

Recently,the increasing interest in wearable technology for personal healthcare and smart virtual/augmented reality applications has led to the development of facile fabrication methods.Lasers have long been used to develop original solutions to such challenging technological problems due to their remote,sterile,rapid,and site-selective processing of materials.In this review,recent developments in relevant laser processes are summarized under two separate categories.First,transformative approaches,such as for laser-induced graphene,are introduced.In addition to design optimization and the alteration of a native substrate,the latest advances under a transformative approach now enable more complex material compositions and multilayer device configurations through the simultaneous transformation of heterogeneous precursors,or the sequential addition of functional layers coupled with other electronic elements.In addition,the more conventional laser techniques,such as ablation,sintering,and synthesis,can still be used to enhance the functionality of an entire system through the expansion of applicable materials and the adoption of new mechanisms.Later,various wearable device components developed through the corresponding laser processes are discussed,with an emphasis on chemical/physical sensors and energy devices.In addition,special attention is given to applications that use multiple laser sources or processes,which lay the foundation for the all-laser fabrication of wearable devices.

Dealuminated Hβ zeolite for selective conversion of fructose to furfural and formic acid

The fructose-to-furfural transformation is facing major challenges in the selectivity and high efficiency. Herein, we have developed a simple and effective approach for the selective conversion of fructose to furfural using Hβ zeolite modified by organic acids for dealuminization to regulate its textural and acidic properties. It was found that citric acid-dealuminized Hβ zeolite possessed high specific surface areas, wide channels and high Brønsted acid amount, which facilitated the selective conversion of fructose to furfural with a maximum yield of 76.2% at433 K for 1 h in the γ-butyrolactone(GBL)-H_(2)O system, as well as the concomitant formation of 83.0% formic acid. The^(13)C-isotope labelling experiments and the mechanism revealed that the selective cleavage of C1–C2 or C5–C6 bond on fructose was firstly occurred to form pentose or C5 intermediate by weak Brønsted acid, which was then dehydrated to furfural by strong Brønsted acid. Also this dealuminized Hβ catalyst showed the great recycling performance and was active for the conversion of glucose and mannose.

Interplay of laser power and pore characteristics in selective laser melting of ZK60 magnesium alloys:A study based on in-situ monitoring and image analysis

This study offers significant insights into the multi-physics phenomena of the SLM process and the subsequent porosity characteristics of ZK60 Magnesium(Mg)alloys.High-speed in-situ monitoring was employed to visualise process signals in real-time,elucidating the dynamics of melt pools and vapour plumes under varying laser power conditions specifically between 40 W and 60 W.Detailed morphological analysis was performed using Scanning-Electron Microscopy(SEM),demonstrating a critical correlation between laser power and pore formation.Lower laser power led to increased pore coverage,whereas a denser structure was observed at higher laser power.This laser power influence on porosity was further confirmed via Optical Microscopy(OM)conducted on both top and cross-sectional surfaces of the samples.An increase in laser power resulted in a decrease in pore coverage and pore size,potentially leading to a denser printed part of Mg alloy.X-ray Computed Tomography(XCT)augmented these findings by providing a 3D volumetric representation of the sample internal structure,revealing an inverse relationship between laser power and overall pore volume.Lower laser power appeared to favour the formation of interconnected pores,while a reduction in interconnected pores and an increase in isolated pores were observed at higher power.The interplay between melt pool size,vapour plume effects,and laser power was found to significantly influence the resulting porosity,indicating a need for effective management of these factors to optimise the SLM process of Mg alloys.

Selective internal radiation therapy segmentectomy:A new minimally invasive curative option for primary liver malignancies?

Transarterial radioembolization or selective internal radiation therapy(SIRT)has emerged as a minimally invasive approach for the treatment of tumors.This percutaneous technique involves the local,intra-arterial delivery of radioactive microspheres directly into the tumor.Historically employed as a palliative measure for liver malignancies,SIRT has gained traction over the past decade as a potential curative option,mirroring the increasing role of radiation segmentectomy.The latest update of the BCLC hepatocellular carcinoma guidelines recognizes SIRT as an effective treatment modality comparable to other local ablative methods,particularly well-suited for patients where surgical resection or ablation is not feasible.Radiation segmentectomy is a more selective approach,aiming to deliver high-dose radiation to one to three specific hepatic segments,while minimizing damage to surrounding healthy tissue.Future research efforts in radiation segmentectomy should prioritize optimizing radiation dosimetry and refining the technique for super-selective administration of radiospheres within the designated hepatic segments.

A novel molybdenite depressant for efficient selective flotation separation of chalcopyrite and molybdenite

A novel small molecule depressant(M-DEP)was used to separate chalcopyrite and molybdenite via flotation.The results showed that M-DEP had an excellent selective depression on molybdenite,while had little effect on the flotation of chalcopyrite.The adsorption capacity of M-DEP on the surface of molybdenite was greater than that on chalcopyrite surface.The adsorption of M-DEP reduced the floatability of molybdenite and had less effect on the floatability of chalcopyrite,which was due to its different adsorption modes on the surface of the two minerals.Furthermore,the interaction between chalcopyrite and M-DEP was mainly chemical interaction,and almost all of the adsorbed M-DEP molecules were removed and replaced by sodium butyl xanthate(SBX).By contrast,hydrophobic interaction was the main way in which M-DEP was adsorbed on the molybdenite surface with little chemical interaction,which was less interfered by SBX addition.Therefore,M-DEP had a super selective depression on molybdenite.The study provided a novel depressant and approach for the deep separation of chalcopyrite and molybdenite via flotation.

Unlocking the potential of ultra-thin two-dimensional antimony materials:Selective growth and carbon coating for efficient potassium-ion storage

Antimony-based anodes have attracted wide attention in potassium-ion batteries due to their high theoretical specific capacities(∼660 mA h g^(-1))and suitable voltage platforms.However,severe capacity fading caused by huge volume change and limited ion transportation hinders their practical applications.Recently,strategies for controlling the morphologies of Sb-based materials to improve the electrochemical performances have been proposed.Among these,the two-dimensional Sb(2D-Sb)materials present excellent properties due to shorted ion immigration paths and enhanced ion diffusion.Nevertheless,the synthetic methods are usually tedious,and even the mechanism of these strategies remains elusive,especially how to obtain large-scale 2D-Sb materials.Herein,a novel strategy to synthesize 2D-Sb material using a straightforward solvothermal method without the requirement of a complex nanostructure design is provided.This method leverages the selective adsorption of aldehyde groups in furfural to induce crystal growth,while concurrently reducing and coating a nitrogen-doped carbon layer.Compared to the reported methods,it is simpler,more efficient,and conducive to the production of composite nanosheets with uniform thickness(3–4 nm).The 2D-Sb@NC nanosheet anode delivers an extremely high capacity of 504.5 mA h g^(-1) at current densities of 100 mA g^(-1) and remains stable for more than 200 cycles.Through characterizations and molecular dynamic simulations,how potassium storage kinetics between 2D Sb-based materials and bulk Sb-based materials are explored,and detailed explanations are provided.These findings offer novel insights into the development of durable 2D alloy-based anodes for next-generation potassium-ion batteries.

Synergy of heterogeneous Co/Ni dual atoms enabling selective C-O bond scission of lignin coupling with in-situ N-functionalization

Selective cleavage of Csp^(2)-OCH_(3)bond in lignin without breaking other types of C-O bonds followed by N-functionalization is fascinating for on-purpose valorization of biomass.Here,a Co/Ni-based dual-atom catalyst CoNiDA@NC prepared by in-situ evaporation and acid-etching of metal species from tailor-made metal–organic frameworks was efficient for reductive upgrading of various lignin-derived phenols to cyclohexanols(88.5%–99.9%yields),which had ca.4 times higher reaction rate than the single-atom catalyst and was superior to state-of-the-art heterogeneous catalysts.The synergistic catalysis of Co/Ni dual atoms facilitated both hydrogen dissociation and hydrogenolysis steps,and could optimize adsorption configuration of lignin-derived methoxylated phenols to further favor the Csp^(2)-OCH_(3)cleavage,as elaborated by theoretical calculations.Notably,the CoNi_(DA)@NC catalyst was highly recyclable,and exhibited excellent demethoxylation performance(77.1%yield)in real lignin monomer mixtures.Via in-situ cascade conversion processes assisted by dual-atom catalysis,various high-value N-containing chemicals,including caprolactams and cyclohexylamines,could be produced from lignin.

Selective adsorption of tetracycline by β-CD-immobilized sodium alginate aerogel coupled with ultrafiltration for reclaimed water

In this work,a novel composite material based on β-cyclodextrin-immobilized sodium alginate aerogel(β-CD/NaAlg) was developed utilizing cross-linker of epichlorohydrin and applied as an adsorbent to remove tetracycline antibiotics from reclaimed wastewater.A series of characterizations were utilized to confirm the successful synthesis of the adsorbent and this β-CD/NaAlg presented a three-dimensional network at the nanoscale or microscale.Under optimal conditions(pH=4,t=8 h,β-CD:NaAlg=9,adsorbent dosage = 1.5 g·L-1),the maximum removal rate of β-CD/NaAlg to tetracycline was 70%.The adsorption behavior of tetracycline on β-CD/NaAlg conformed to the Freundlich isotherm model(R2=0.9977) and the pseudo-second-order kinetic model(R^(2)=0.9993).Moreover,the adsorbent still removed 55.3% of tetracycline after five cycles.Specially,the adsorbent was integrated with ultrafiltration to adsorb tetracycline antibiotics from simulated reclaimed wastewater,and the removal rate of tetracycline reached 78.9% within 2 h.The existence of Cr(Ⅵ) had a negligible impact on tetracycline removal,while the presence of humic acid exhibited a promoting effect.The possible adsorption mechanisms were also elucidated through X-ray photoelectron spectroscopy and density functional theory analysis.In summary,β-CD/NaAlg represents an environmentally friendly,efficient,and sustainable adsorbent for removing tetracycline antibiotics from reclaimed water.

High-strength and thermally stable TiB_(2)-modified Al-Mn-Mg-Er-Zr alloy fabricated via selective laser melting

To increase the processability and plasticity of the selective laser melting(SLM)fabricated Al-Mn-Mg-Er-Zr alloys,a novel TiB_(2)-modified Al-Mn-Mg-Er-Zr alloy with a mixture of Al-Mn-Mg-Er-Zr and nano-TiB_(2) powders was fabricated by SLM.The pro-cessability,microstructure,and mechanical properties of the alloy were systematically investigated by density measurement,microstruc-ture characterization,and mechanical properties testing.The alloys fabricated at 250 W displayed higher relative densities due to a uni-formly smooth top surface and appropriate laser energy input.The maximum relative density value of the alloy reached(99.7±0.1)%,demonstrating good processability.The alloy exhibited a duplex grain microstructure consisting of columnar regions primarily and equiaxed regions with TiB_(2),Al6Mn,and Al3Er phases distributed along the grain boundaries.After directly aging treatment at a high tem-perature of 400℃,the strength of the SLM-fabricated TiB_(2)/Al-Mn-Mg-Er-Zr alloy increased due to the precipitation of the secondary Al6Mn phases.The maximum yield strength and ultimate tensile strength of the aging alloy were measured to be(374±1)and(512±13)MPa,respectively.The SLM-fabricated TiB_(2)/Al-Mn-Mg-Er-Zr alloy demonstrates exceptional strength and thermal stability due to the synergistic effects of the inhibition of grain growth,the incorporation of TiB_(2) nanoparticles,and the precipitation of secondary Al6Mn nanoparticles.

Strength and plasticity improvement induced by strong grain refinement after Zr alloying in selective laser-melted AlSiMg1.4 alloy

In order to enhance the mechanical properties of the selective laser-melted(SLM) high-Mg content AlSiMg1.4 alloy,the Zr element was introduced.The influence of Zr alloying on the processability,microstructure,and mechanical properties of the alloy was systematically investigated through performing microstructure analysis and tensile testing.It was demonstrated that the SLM-fabricated AlSiMg1.4-Zr alloy exhibited high process stability with a relative density of over 99.5% at various process parameters.Besides,the strong grain refinement induced by the primary Al3Zr particle during the melt solidification process simultaneously enhanced both the strength and plasticity of the alloy.The values for the yield strength,ultimate tensile strength,and elongation of the SLM-fabricated AlSiMg1.4-Zr were(343±3) MPa,(485±4) MPa,and(10.2±0.2)%,respectively,demonstrating good strengthplasticity synergy in comparison to the AlSiMg1.4 and other Al-Si-based alloys fabricated by SLM.

A Selective‑Response Hypersensitive Bio‑Inspired Strain Sensor Enabled by Hysteresis Effect and Parallel Through‑Slits Structures

Flexible strain sensors are promising in sensing minuscule mechanical signals,and thereby widely used in various advanced fields.However,the effective integration of hypersensitivity and highly selective response into one flexible strain sensor remains a huge challenge.Herein,inspired by the hysteresis strategy of the scorpion slit receptor,a bio-inspired flexible strain sensor(BFSS)with parallel through-slit arrays is designed and fabricated.Specifically,BFSS consists of conductive monolayer graphene and viscoelastic styrene–isoprene–styrene block copolymer.Under the synergistic effect of the bio-inspired slit structures and flexible viscoelastic materials,BFSS can achieve both hypersensitivity and highly selective frequency response.Remarkably,the BFSS exhibits a high gage factor of 657.36,and a precise identification of vibration frequencies at a resolution of 0.2 Hz through undergoing different morphological changes to high-frequency vibration and low-frequency vibration.Moreover,the BFSS possesses a wide frequency detection range(103 Hz)and stable durability(1000 cycles).It can sense and recognize vibration signals with different characteristics,including the frequency,amplitude,and waveform.This work,which turns the hysteresis effect into a"treasure,"can provide new design ideas for sensors for potential applications including human–computer interaction and health monitoring of mechanical equipment.

Aqueous electrochemical delithiation of cathode materials as a strategy to selectively recover lithium from waste lithium-ion batteries

Lithium recovery from end-of-life Li-ion batteries(LIBs)through pyro-and hydrometallurgical recycling processes involves several refining stages,with high consumption of reagents and energy.A competitive technological alternative is the electrochemical oxidation of the cathode materials,whereby lithium can be deintercalated and transferred to an electrolyte solution without the aid of chemical extracting compounds.This article investigates the potential to selectively recover Li from LIB cathode materials by direct electrochemical extraction in aqueous solutions.The process allowed to recovering up to 98%of Li from high-purity commercial cathode materials(LiMn_(2)O_(4),LiCoO_(2),and Li Ni_(1/3)Mn_(1/3)Co_(1/3)O_(2))with a faradaic efficiency of 98%and negligible co-extraction of Co,Ni,and Mn.The process was then applied to recover Li from the real waste LIBs black mass obtained by the physical treatment of electric vehicle battery packs.This black mass contained graphite,conductive carbon,and metal impurities from current collectors and steel cases,which significantly influenced the evolution and performances of Li electrochemical extraction.Particularly,due to concomitant oxidation of impurities,lithium extraction yields and faradaic efficiencies were lower than those obtained with high-purity cathode materials.Copper oxidation was found to occur within the voltage range investigated,but it could not quantitatively explain the reduced Li extraction performances.In fact,a detailed investigation revealed that above 1.3 V vs.Ag/Ag Cl,conductive carbon can be oxidized,contributing to the decreased Li extraction.Based on the reported experimental results,guidelines were provided that quantitatively enable the extraction of Li from the black mass,while preventing the simultaneous oxidation of impurities and,consequently,reducing the energy consumption of the proposed Li recovery method.

Synergistic strengthening mechanism of Ca^(2+)-sodium silicate to selective separation of feldspar and quartz

Inhibitors are important for flotation separation of quartz and feldspar.In this study,a novel combined inhibitor was used to separate quartz and feldspar in near-neutral pulp.Selective inhibition of the combined inhibitor was assessed by micro-flotation experiments.And a series of detection methods were used to detect differences in the surface properties of feldspars and quartz after flotation reagents and put forward the synergistic strengthening mechanism.The outcomes were pointed out that pre-mixing combined inhibitors were more effective than the addition of Ca^(2+)and SS in sequence under the optimal proportion of 1:5.A concentrate from artificial mixed minerals that was characterized by a high quartz grade and a high recovery was acquired,and was found to be 90.70wt% and 83.70%,respectively.It was demonstrated that the combined inhibitor selectively prevented the action of the collector and feldspar from Fourier-transform infrared(FT-IR)and adsorption capacity tests.The results of X-ray photoelectron spectroscopy(XPS)indicated that Ca^(2+)directly interacts with the surface of quartz to increase the adsorption of collectors.In contrast,the chemistry property of Al on the feldspar surface was altered by combined inhibitor due to Na^(+)and Ca^(2+)taking the place of K^(+),resulting in the composite inhibitor forms a hydrophilic structure,which prevents the adsorption of the collector on the surface of feldspar by interacting with the Al active site.The combination of Ca^(2+)and SS synergically strengthens the difference of collecting property between quartz and feldspar by collector,thus achieving the effect of efficient separation.A new strategy for flotation to separate quartz from feldspar in near-neutral pulp was provided.

Effects of processing parameters on fabrication defects,microstructure and mechanical properties of additive manufactured Mg–Nd–Zn–Zr alloy by selective laser melting process

Mg–3Nd–0.2Zn–0.4Zr(NZ30K,wt.%)alloy is a new kind of high-performance metallic biomaterial.The combination of the NZ30K Magnesium(Mg)alloy and selective laser melting(SLM)process seems to be an ideal solution to produce porous Mg degradable implants.However,the microstructure evolution and mechanical properties of the SLMed NZ30K Mg alloy were not yet studied systematically.Therefore,the fabrication defects,microstructure,and mechanical properties of the SLMed NZ30K alloy under different processing parameters were investigated.The results show that there are two types of fabrication defects in the SLMed NZ30K alloy,gas pores and unfused defects.With the increase of the laser energy density,the porosity sharply decreases to the minimum first and then slightly increases.The minimum porosity is 0.49±0.18%.While the microstructure varies from the large grains with lamellar structure inside under low laser energy density,to the large grains with lamellar structure inside&the equiaxed grains&the columnar grains under middle laser energy density,and further to the fine equiaxed grains&the columnar grains under high laser energy density.The lamellar structure in the large grain is a newly observed microstructure for the NZ30K Mg alloy.Higher laser energy density leads to finer grains,which enhance all the yield strength(YS),ultimate tensile strength(UTS)and elongation,and the best comprehensive mechanical properties obtained are YS of 266±2.1 MPa,UTS of 296±5.2 MPa,with an elongation of 4.9±0.68%.The SLMed NZ30K Mg alloy with a bimodal-grained structure consisting of fine equiaxed grains and coarser columnar grains has better elongation and a yield drop phenomenon.

Selective leaching of lithium from spent lithium-ion batteries using sulfuric acid and oxalic acid

Traditional hydrometallurgical methods for recovering spent lithium-ion batteries(LIBs)involve acid leaching to simultaneously extract all valuable metals into the leachate.These methods usually are followed by a series of separation steps such as precipitation,extraction,and stripping to separate the individual valuable metals.In this study,we present a process for selectively leaching lithium through the synergistic effect of sulfuric and oxalic acids.Under optimal leaching conditions(leaching time of 1.5 h,leaching temperature of 70°C,liquid-solid ratio of 4 mL/g,oxalic acid ratio of 1.3,and sulfuric acid ratio of 1.3),the lithium leaching efficiency reached89.6%,and the leaching efficiencies of Ni,Co,and Mn were 12.8%,6.5%,and 21.7%.X-ray diffraction(XRD)and inductively coupled plasma optical emission spectrometer(ICP-OES)analyses showed that most of the Ni,Co,and Mn in the raw material remained as solid residue oxides and oxalates.This study offers a new approach to enriching the relevant theory for selectively recovering lithium from spent LIBs.

Cu,N codoped carbon nanosheets encapsulating ultrasmall Cu nanoparticles for enhancing selective 1,2-propanediol oxidation

In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited oxygen reduction rate and easy C-C cleavage.Given the high economic feasibility of nonnoble metals,i.e.,Cu,in this work,copper and nitrogen codoped porous carbon nanosheets encapsulating ultrafine Cu nanoparticles(Cu@Cu-N-C)were developed to realize highly selective of PDO oxidation to LA.The carbon-encapsulated ultrasmall Cu^(0)NPs in Cu@Cu-N-C have high PDO dehydrogenation activity while N-coordinated Cu(Cu-N)sites are responsible for the high oxygen reduction efficacy.Therefore,the performance of catalytic PDO conversion to LA is optimized by a proposed pathway of PDO→hydroxylacetone→lactaldehyde→LA.Specifically,the enhanced LA selectivity is 88.5%,and the PDO conversion is up to 75.1%in an O_(2)-pressurized reaction system(1.0 MPa O_(2)),superior to other Cu-based catalysts,while in a milder nonpressurized system(O_(2)flow rate of 100 mL min-1),a remarkable LA selectivity(94.2%)is obtained with 39.8%PDO conversion,2.2 times higher than that of supported Au nanoparticles(1%Au/C).Moreover,carbon encapsulation offers Cu@Cu-N-C with strong leaching resistance for better recycling.

Effect of an Airbag-selective Portal Vein Blood Arrester on the Liver after Hepatectomy:A New Technique for Selective Clamping of the Portal Vein

Objective:A novel technique was explored using an airbag-selective portal vein blood arrester that circumvents the need for an intraoperative assessment of anatomical variations in patients with complex intrahepatic space-occupying lesions.Methods:Rabbits undergoing hepatectomy were randomly assigned to 4 groups:intermittent portal triad clamping(PTC),intermittent portal vein clamping(PVC),intermittent portal vein blocker with an airbag-selective portal vein blood arrester(APC),and without portal blood occlusion(control).Hepatic ischemia and reperfusion injury were assessed by measuring the 7-day survival rate,blood loss,liver function,hepatic pathology,hepatic inflammatory cytokine infiltration,hepatic malondialdehyde levels,and proliferating cell nuclear antigen levels.Results:Liver damage was substantially reduced in the APC and PVC groups.The APC animals exhibited transaminase levels similar to or less oxidative stress damage and inflammatory hepatocellular injury compared to those exhibited by the PVC animals.Bleeding was significantly higher in the control group than in the other groups.The APC group had less bleeding than the PVC group because of the avoidance of portal vein skeletonization during hepatectomy.Thus,more operative time was saved in the APC group than in the PVC group.Moreover,the total 7-day survival rate in the APC group was higher than that in the PTC group.Conclusion:Airbag-selective portal vein blood arresters may help protect against hepatic ischemia and reperfusion injury in rabbits undergoing partial hepatectomy.This technique may also help prevent liver damage in patients requiring hepatectomy.

Regulating the oxidation state of Pd to enhance the selective hydrogenation for 5-hydroxymethylfurfural

The highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran is an important reaction in the field of biomass hydrogenation,because it is a bridge between biomass resources and chemical industry.Here,we precisely constructed carbon nitride supported Pd-based catalysts by a simple impregnation-reduction method.By changing the reduction temperature,catalysts with different oxidation state could be precisely constructed.Moreover,the important correlation between the ratio of Pd^(0)/Pd^(2+)and catalytic activity is revealed during the selective hydrogenation of HMF.The Pd/g—C_(3)N_(4)—300 catalyst with a Pd^(0)/Pd^(2+)ratio of 3/2 showed the highest catalytic activity,which could get 96.9%5-hydroxymethylfurfural conversion and 90.3%2,5-dihydroxymethylfuran selectivity.Further density functional theory calculation revealed that the synergistic effect between Pd0and Pd2+in Pd/g—C_(3)N_(4)—300 system could boost the adsorption of the substrate and the dissociation of hydrogen.In this work,we highlight the important correlation between metal oxidation state and catalytic activity,which provides valuable insights for the rational design of precious metal catalysts for hydrogenation reactions.

Internal electric field modulation by copper vacancy concentration of cuprous sulfide nanosheets for enhanced selective CO_(2) photoreduction

Although the internal electric field(IEF)of photocatalysts is acknowledged as a potent driving force for photocharge separation,modulating the IEF intensity to achieve enhanced photocatalytic performances remains a challenge.Herein,cuprous sulfide nanosheets with different Cu vacancy concentration were employed to study IEF modulation and corresponding direct charge transfer.Among the samples,Cu_(1.8)S nanosheets possessed intensified IEF intensity compared with those of Cu_(2)S and Cu_(1.95)S nanosheets,suggesting that an enhanced IEF intensity could be achieved by introducing more Cu vacancies.This intensified IEF of Cu_(1.8)S nanosheets induced numerous photogenerated electrons to migrate to its surface,and the dissociative electrons were then captured by Cu vacancies,resulting in efficient charge separation spatially.In addition,the Cu vacancies on Cu_(1.8)S nanosheets accumulated electrons as active sites to lower the energy barrier of rate-determining step of CO_(2)photoreduction,leading to the selective conversion of CO_(2)to CO.Herein,the manipulation of IEF intensity through Cu vacancy concentration regulation of cuprous sulfide photocatalysts for efficient charge separation has been discussed,providing a scientific strategy to rationally improve photocata lytic performances for solar energy conversion.