Laser‑Induced and MOF‑Derived Metal Oxide/Carbon Composite for Synergistically Improved Ethanol Sensing at Room temperature

Advancements in sensor technology have significantly enhanced atmospheric monitoring.Notably,metal oxide and carbon(MO_(x)/C)hybrids have gained attention for their exceptional sensitivity and room-temperature sensing performance.However,previous methods of synthesizing MO_(x)/C composites suffer from problems,including inhomogeneity,aggregation,and challenges in micropatterning.Herein,we introduce a refined method that employs a metal–organic framework(MOF)as a precursor combined with direct laser writing.The inherent structure of MOFs ensures a uniform distribution of metal ions and organic linkers,yielding homogeneous MO_(x)/C structures.The laser processing facilitates precise micropatterning(<2μm,comparable to typical photolithography)of the MO_(x)/C crystals.The optimized MOF-derived MO_(x)/C sensor rapidly detected ethanol gas even at room temperature(105 and 18 s for response and recovery,respectively),with a broad range of sensing performance from 170 to 3,400 ppm and a high response value of up to 3,500%.Additionally,this sensor exhibited enhanced stability and thermal resilience compared to previous MOF-based counterparts.This research opens up promising avenues for practical applications in MOF-derived sensing devices.

MIL-100(V) derived porous vanadium oxide/carbon microspheres with oxygen defects and intercalated water molecules as high-performance cathode for aqueous zinc ion battery

The development of aqueous zinc ion battery cathode materials with high capacity and high magnification is still a challenge.Herein,porous vanadium oxide/carbon(p-VO_(x)@C,mainly VO_(2) with a small amount of V_(2)O_(3)) core/shell microspheres with oxygen vacancies are facilely fabricated by using a vanadium-based metal-organic framework(MIL-100(V)) as a sacrificial template.This unique structure can improve the conductivity of the VO_(x),accelerate electrolyte diffusion,and suppress structural collapse during circulation.Subsequently,H_(2)O molecules are introduced into the interlayer of VO_(x) through a highly efficient in-situ electrochemical activation process,facilitating the intercalation and diffusion of zinc ions.After the activation,an optimal sample exhibits a high specific capacity of 464.3 mA h g^(-1) at0.2 A g^(-1) and 395.2 mA h g^(-1) at 10 A g^(-1),indicating excellent rate performance.Moreover,the optimal sample maintains a capacity retention of about 89.3% after 2500 cycles at 10 A g^(-1).Density functional theory calculation demonstrates that the presence of oxygen vacancies and intercalated water molecules can significantly reduce the diffusion barrier for zinc ions.In addition,it is proved that the storage of zinc ions in the cathode is achieved by reversible intercalation/extraction during the charge and discharge process through various ex-situ analysis technologies.This work demonstrates that the p-VO_(x)@C has great potential for applications in aqueous ZIBs after electrochemical activation.

Carbon Monoxide Modulates Auxin Transport and Nitric Oxide Signaling in Plants under Iron Deficiency Stress

Carbon monoxide(CO)and nitric oxide(NO)are signal molecules that enhance plant adaptation to environmental stimuli.Auxin is an essential phytohormone for plant growth and development.CO and NO play crucial roles in modulating the plant’s response to iron deficiency.Iron deficiency leads to an increase in the activity of heme oxygenase(HO)and the subsequent generation of CO.Additionally,it alters the polar subcellular distribution of Pin-Formed 1(PIN1)proteins,resulting in enhanced auxin transport.This alteration,in turn,leads to an increase in NO accumulation.Furthermore,iron deficiency enhances the activity of ferric chelate reductase(FCR),as well as the expression of the Fer-like iron deficiency-induced transcription factor 1(FIT)and the ferric reduction oxidase 2(FRO2)genes in plant roots.Overexpression of the long hypocotyl 1(HY1)gene,which encodes heme oxygenase,or the CO donor treatment resulted in enhanced basipetal auxin transport,higher FCR activity,and the expression of FIT and FRO2 genes under Fe deficiency.Here,a potential mechanism is proposed:CO and NO interact with auxin to address iron deficiency stress.CO alters auxin transport,enhancing its accumulation in roots and up-regulating key iron-related genes like FRO2 and IRT1.Elevated auxin levels affect NO signaling,leading to greater sensitivity in root development.This interplay promotes FCR activity,which is crucial for iron absorption.Together,these molecules enhance iron uptake and root growth,revealing a novel aspect of plant physiology in adapting to environmental stress.

Proof of Aerobically Autoxidized Self-Charge Concept Based on Single Catechol-Enriched Carbon Cathode Material

The self-charging concept has drawn considerable attention due to its excellent ability to achieve environmental energy harvesting,conversion and storage without an external power supply.However,most self-charging designs assembled by multiple energy harvesting,conversion and storage materials increase the energy transfer loss;the environmental energy supply is generally limited by climate and meteorological conditions,hindering the potential application of these selfpowered devices to be available at all times.Based on aerobic autoxidation of catechol,which is similar to the electrochemical oxidation of the catechol groups on the carbon materials under an electrical charge,we proposed an air-breathing chemical self-charge concept based on the aerobic autoxidation of catechol groups on oxygen-enriched carbon materials to ortho-quinone groups.Energy harvesting,conversion and storage functions could be integrated on a single carbon material to avoid the energy transfer loss among the different materials.Moreover,the assembled Cu/oxygen-enriched carbon battery confirmed the feasibility of the air-oxidation self-charging/electrical discharging mechanism for potential applications.This air-breathing chemical self-charge concept could facilitate the exploration of high-efficiency sustainable air self-charging devices.

Porous metal oxides in the role of electrochemical CO_(2) reduction reaction

The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.

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.

Pulsed electrolysis of carbon dioxide by large-scale solid oxide electrolytic cells for intermittent renewable energy storage

CO_(2) electrolysis with solid oxide electrolytic cells(SOECs)using intermittently available renewable energy has potential applications for carbon neutrality and energy storage.In this study,a pulsed current strategy is used to replicate intermittent energy availability,and the stability and conversion rate of the cyclic operation by a large-scale flat-tube SOEC are studied.One hundred cycles under pulsed current ranging from -100 to -300 mA/cm^(2) with a total operating time of about 800 h were carried out.The results show that after 100 cycles,the cell voltage attenuates by 0.041%/cycle in the high current stage of−300 mA/cm^(2),indicating that the lifetime of the cell can reach up to about 500 cycles.The total CO_(2) conversion rate reached 52%,which is close to the theoretical value of 54.3% at -300 mA/cm^(2),and the calculated efficiency approached 98.2%,assuming heat recycling.This study illustrates the significant advantages of SOEC in efficient electrochemical energy conversion,carbon emission mitigation,and seasonal energy storage.

Sub-2 nm mixed metal oxide for electrochemical reduction of carbon dioxide to carbon monoxide

Mixed metal oxide(MMO) represents a critical class of materials that can allow for obtaining a dynamic interface between its components:reduced metal and its metal oxide counterpart during an electrocatalytic reaction.Here,a synthetic method utilizing a MOF-derived micro/mesoporous carbon as a template to prepare sub-2 nm MMO catalysts for CO_(2) electro reduction is reported.Starting from the zeolite imidazolate framework(ZIF-8),the pyrolyzed derivatives were used to synthesize sub-2 nm Pd-Ni MMO with different compositions.The Ni-rich(Pd_(20)-Ni_(80)/ZC) catalyst exhibits unexpectedly superior performance for CO production with an improved Faradaic efficiency(FE) of 95.3% at the current density of 200 mA cm^(-2) at-0.56 V vs.reversible hydrogen electrode(RHE) compared to other Pd-Ni compositions.X-ray photoelectron spectroscopy(XPS) analysis confirms the presence of Ni^(2+) and Pd^(2+) in all compositions,demonstrating the presence of MMO.Density functional theory(DFT) calculation reveals that the lower CO binding energy on the surface of the Pd_(20)-Ni_(80) cluster eases CO desorption,thus increasing its production.This work provides a general synthetic strategy for MMO electrocatalysts and can pave a new way for screening multimetallic catalysts with a dynamic electrochemical interface.

Mechanically flexible reduced graphene oxide/carbon composite films for high-performance quasi-solid-state lithium-ion capacitors

Practical applications of diverse flexible wearable electronics require electrochemical energy storage(EES)devices with multiple configurations.Moreover,to fabricate flexible EES devices with high energy density and stability,organic integration from electrode design to device assembly is required.To address these challenges,a free-standing reduced graphene oxide(rGO)/carbon film with a unique sandwich structure has been designed via the assistance of vacuum-assistant filtration for lithium-ion capacitors(LICs).The graphene acts as not only a binder to construct a three-dimensional conductive network but also an active material to provide additional capacitive lithium storage sites,thus enabling fast ion/electron transport and improving the capacity.The designed rGO/hard carbon(rGO/HC)and rGO/activated carbon(rGO/AC)free-standing films exhibit enhanced specific capacities(513.7 mA h g^(-1)for rGO/HC and 102.8 mA h g^(-1)for rGO/AC)and excellent stability.Moreover,the integrated flexible quasi-solid-state rGO/AC//rGO/HC LIC devices possess a maximum energy density of 138.3 Wh kg^(-1),a high power density of 11 kW kg^(-1),and improved cycling performance(84.4%capacitance maintained after 10,000 cycles),superior to the AC//HC LIC(43.5%retention).Such a strategy enlightens the development of portable flexible LICs.

Finned Zn-MFI zeolite encapsulated noble metal nanoparticle catalysts for the oxidative dehydrogenation of propane with carbon dioxide

Oxidative dehydrogenation of propane with carbon dioxide(CO_(2)-ODP)characterizes the tandem dehydrogenation of propane to propylene with the reduction of the greenhouse gas of CO_(2)to valuable CO.However,the existing catalyst is limited due to the poor activity and stability,which hinders its industrialization.Herein,we design the finned Zn-MFI zeolite encapsulated noble metal nanoparticles(NPs)as bifunctional catalysts(NPs@Zn-MFI)for CO_(2)-ODP.Characterization results reveal that the Zn2+species are coordinated with the MFI zeolite matrix as isolated cations and the NPs of Pt,Rh,or Rh Pt are highly dispersed in the zeolite crystals.The isolated Zn2+cations are very effective for activating the propane and the small NPs are favorable for activating the CO_(2),which synergistically promote the selective transformation of propane and CO_(2)to propylene and CO.As a result,the optimal 0.25%Rh0.50%Pt@Zn-MFI catalyst shows the best propylene yield,satisfactory CO_(2)conversion,and long-term stability.Moreover,considering the tunable synergetic effects between the isolated cations and NPs,the developed approach offers a general guideline to design more efficient CO_(2)-ODP catalysts,which is validated by the improved performance of the bifunctional catalysts via simply substituting Sn4+cations for Zn2+cations in the MFI zeolite matrix.

Effect of carbon dioxide on oxy-fuel combustion of hydrogen sulfide:An experimental and kinetic modeling

CO_(2) is an important component in the acid gas and it is necessary to study the effect of CO_(2) presence on the oxy-fuel combustion of H_(2)S with particular focus on the formation of carbonyl sulfide(COS).The oxyfuel combustion of acid gas was conducted in a coaxial jet double channel burner.The distribution of flame temperature and products under stoichiometric condition along axial(R=0.0)and radial at about 3.0 mm(R=0.75)were analyzed,respectively.The Chemkin-Pro software was used to analyze the rate of production(ROP)for gas products and the reaction pathway of acid gas combustion.Both experimental and simulation results showed that acid gas combustion experienced the H2S chemical decomposition,H_(2)S oxidation and accompanied by H_(2) oxidation.The CO_(2) presence reduced the peak flame temperature and triggered the formation of COS in the flame area.COS formation at R=0.0 was mainly through the reaction of CO_(2) and CO with sulfur species,whereas at R=0.75 it was through the reaction of CO with sulfur species.The ROP results indicated that H_(2) was mainly from H_(2)O decomposition in the H_(2)S oxidation stage,and COS was formed by the reaction of CO_(2) with H_(2)S.ROP and other detailed analysis further revealed the role of H,OH and SH radicals in each stage of H_(2)S conversion.This study revealed the COS formation mechanisms with CO_(2) presence in the oxy-fuel combustion of H_(2)S and could offer important insights for pollutant control.

Oxidative exfoliation of spent cathode carbon:A two-in-one strategy for its decontamination and high-valued application

Spent cathode carbon(SCC)from aluminum electrolysis is a potential graphite resource.However,full use of the SCC remains a challenge,since it contains many hazardous substances(e.g.,fluoride salts,cyanides),encapsulated within the thick carbon layers and thus posing serious environmental concerns.This work presents a chemical oxidative exfoliation route to achieve the recycling of SCC and the decontaminated SCC with high-valued graphene oxide(GO)-like carbon structures(SCC-GO)is applied as an excellent adsorbent for organic pollutants.Specifically,after the oxidative exfoliation,the embedded hazardous constituents are fully exposed,facilitating their subsequent removal by aqueous leaching.Moreover,benefiting from the enhanced specific surface areas along with abundant O-containing functional groups,the as-produced SCC-GO,shows an adsorption capacity as high as 347 mg·g^(-1)when considering methylene blue as a pollutant model,which exceeds most of the recently reported carbon-based adsorbents.Our study provides a feasible solution for the efficient recycling of hazardous carbonaceous wastes.

Preparation and Characterization of Y-type Carbon Nanotubes by Using Anodized Alumina Oxide (AAO) Template

利用两步氧化法,通过对氧化直流电压进行周期性调制可制备出带有Y型孔道的氧化铝模板;然后以金属钴为催化剂,乙炔为碳源,通过CVD法制取得到具有规则Y型分支的碳纳米管阵列.已制备出的碳管分支角度在20°～120°的范围内.实验表明,两段分支所成的角度以及分支的长度与合成氧化铝模板的脉冲电压调节规律有关,短脉冲,高氧化电压有利于生长出的短而密集的分支构型.

Synthesis of cyclic carbonates from epoxides or olefins and CO_2 catalyzed by metal-organic frameworks and quaternary ammonium salts

Catalytic properties of the metal-organic framework Cr-MIL-101 in solvent-free cycloaddition of CO2 to epoxides to produce cyclic carbon- ates using tetrabutylammonium bromide as co-catalyst have been explored under mild reaction conditions （8 bar CO2, 25 ~C）. Styrene and propylene carbonates were formed with high yields （95% and 82%, respectively）. Catalytic performance of Cr-MIL-101 was compared with other MOFs： Fe-MIL-101, Zn-MOF-5 and HKUST-1, The catalytic properties of different quaternary ammonium bromides, Cr-MIL-101 as well as PW12/Cr-MIL-101 composite material have been assessed in oxidative carboxylation of styrene in the presence of both tert-butyl hydroperoxide and H202 as oxidants at 8-100bar CO2 and 25-80 ~C with selectivity to styrene carbonate up to 44% at 57% substrate conversion.

Effects of Irrigation on Nitrous Oxide,Methane and Carbon Dioxide Fluxes in an Inner Mongolian Steppe

Increased precipitation during the vegetation periods was observed in and further predicted for Inner Mongolia. The changes in the associated soil moisture may affect the biosphere-atmosphere exchange of greenhouse gases. Therefore, we set up an irrigation experiment with one watered （W） and one unwatered plot （UW） at a winter-grazed Leymus chinensis-steppe site in the Xilin River catchment, Inner Mongolia. UW only received the natural precipitation of 2005 （129 mm）, whereas W was additionally watered after the precipitation data of 1998 （in total 427 mm）. In the 3-hour resolution, we determined nitrous oxide （N20）, methane （CH4） and carbon dioxide （CO2） fluxes at both plots between May and September 2005, using a fully automated, chamber-based measuring system. N20 fluxes in the steppe were very low, with mean emissions （±s.e.） of 0.9-4-0.5 and 0.7-4-0.5 μg N m^-2 h^-1 at W and UW, respectively. The steppe soil always served as a CH4 sink, with mean fluxes of -24.1-4-3.9 and -31.1-4- 5.3 μg C m^-2 h^-1 at W and UW. Nighttime mean CO2 emissions were 82.6±8.7 and 26.3±1.7 mg C m^-2 h^-1 at W and UW, respectively, coinciding with an almost doubled aboveground plant biomass at W. Our results indicate that the ecosystem CO2 respiration responded sensitively to increased water input during the vegetation period, whereas the effects on CH4 and N2O fluxes were weak, most likely due to the high evapotranspiration and the lack of substrate for N2O producing processes. Based on our results, we hypothesize that with the gradual increase of summertime precipitation in Inner Mongolia, ecosystem CO2 respiration will be enhanced and CH4 uptake by the steppe soils will be lightly inhibited.

Toxicity of Multi-Walled Carbon Nanotubes,Graphene Oxide,and Reduced Graphene Oxide to Zebrafish Embryos

Objective This study was aimed to investigate the toxic effects of 3 nanomaterials, i.e. multi-walled carbon nanotubes （MWCNTs）, graphene oxide （GO）, and reduced graphene oxide （RGO）, on zebrafish embryos. Methods The 2-h post-fertilization （hpf） zebrafish embryos were exposed to MWCNTs, GO, and RGO at different concentrations （1, 5, 10, 50, 100 mg/L） for 96 h. Afterwards, the effects of the 3 nanomateria on spontaneous movement, heart rate, hatching rate, length of larvae, mortality, and malformations Is were evaluated. Results Statistical analysis indicated that RGO significantly inhibited the hatching of zebrafish embryos. Furthermore, RGO and MWCNTs decreased the length of the hatched larvae at 96 hpf. No obvious morphological malformation or mortality was observed in the zebrafish embryos after exposure to the three nanomaterials. Conclusion MWCNTs, GO, and RGO were all toxic to zebrafish embryos to influence embryos hatching and larvae length. Although no obvious morphological malformation and mortality were observed in exposed zebrafish embryos, further studies on the toxicity of the three nanomaterials are still needed.

Catalytic reduction of nitric oxide with carbon monoxide on copper-cobalt oxides supported on nano-titanium dioxide

A series of copper-cobalt oxides supported on nano-titanium dioxide were prepared for the reduction of nitric oxide with carbon monoxide and characterized using techniques such as XRD, BET and TPR. Catalyst CuCoOx/TiO2 with Cu/Co molar ratio of 1/2, CuCo total loading of 30% at the calcination temperature of 350℃ formed CuCo204 spinel and had the highest activity. NO conversion reached 98.9% at 200℃. Mechanism of the reduction was also investigated, N20 was mainly yielded below 100℃, while N2 was produced instead at higher temperature. O2 was supposed to accelerate the reaction between NOx and CO for its oxidation of NO to give more easily reduced NO2, but the oxidation of CO by O2 to CO2 decreased the speed of the reaction greatly. Either SO2 or H20 had no adverse impact on the activity of NO reduction; however, in the presence of both SO2 and H20, the catalyst deactivated quickly.

Screening of MgO- and CeO_2-Based Catalysts for Carbon Dioxide Oxidative Coupling of Methane to C_(2+) Hydrocarbons

The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM) have been investigated over ternary and binary metal oxide catalysts. The catalysts are prepared by doping MgO- and CeO2-based solids with oxides from alkali (Li2O), alkaline earth (CaO), and transition metal groups (WO3 or MnO). The presence of the peroxide (O2-2) active sites on the Li2O2, revealed by Raman spectroscopy, may be the key factor in the enhanced performance of some of the Li2O/MgO catalysts. The high reducibility of the CeO2 catalyst, an important factor in the CO2-OCM catalyst activity, may be enhanced by the presence of manganese oxide species. The manganese oxide species increases oxygen mobility and oxygen vacancies in the CeO2 catalyst. Raman and Fourier Transform Infra Red (FT-IR) spectroscopies revealed the presence of lattice vibrations of metal-oxygen bondings and active sites in which the peaks corresponding to the bulk crystalline structures of Li2O, CaO, WO3 and MnO are detected. The performance of 5%MnO/15%CaO/CeO2 catalyst is the most potential among the CeO2-based catalysts, although lower than the 2%Li2O/MgO catalyst. The 2%Li2O/MgO catalyst showed the most promising C2+ hydrocarbons selectivity and yield at 98.0% and 5.7%, respectively.

Lightweight,Flexible Cellulose-Derived Carbon Aerogel@Reduced Graphene Oxide/PDMS Composites with Outstanding EMI Shielding Performances and Excellent Thermal Conductivities

In order to ensure the operational reliability and infor-mation security of sophisticated electronic components and to protect human health,efficient electromagnetic interference(EMI)shielding materials are required to attenuate electromagnetic wave energy.In this work,the cellulose solution is obtained by dissolving cotton through hydrogen bond driving self-assembly using sodium hydroxide(NaOH)/urea solution,and cellulose aerogels(CA)are prepared by gelation and freeze-drying.Then,the cellulose carbon aerogel@reduced graphene oxide aerogels(CCA@rGO)are prepared by vacuum impregnation,freeze-drying followed by thermal annealing,and finally,the CCA@rGO/polydimethylsiloxane(PDMS)EMI shielding composites are prepared by backfilling with PDMS.Owing to skin-core structure of CCA@rGO,the complete three-dimensional(3D)double-layer con-ductive network can be successfully constructed.When the loading of CCA@rGO is 3.05 wt%,CCA@rGO/PDMS EMI shielding composites have an excellent EMI shielding effectiveness(EMI SE)of 51 dB,which is 3.9 times higher than that of the co-blended CCA/rGO/PDMS EMI shielding composites(13 dB)with the same loading of fillers.At this time,the CCA@rGO/PDMS EMI shielding composites have excellent thermal stability(T_(HRI) of 178.3℃)and good thermal conductivity coefficient(λ of 0.65 W m^(-1) K^(-1)).Excellent comprehensive performance makes CCA@rGO/PDMS EMI shielding composites great prospect for applications in lightweight,flexible EMI shielding composites.