In search of environmentally benign compounds with high biological activity, low toxicity and low resistance, 8 novel benzoyl hydrazines containing pyrazole were designed and synthesized. All compounds were characteri...In search of environmentally benign compounds with high biological activity, low toxicity and low resistance, 8 novel benzoyl hydrazines containing pyrazole were designed and synthesized. All compounds were characterized by I H NMR spectra and HRMS. The preliminary results of biological activity assessment indicated that most of title compounds exhibited certain insecticidal activities against M）,thimna separata Walker at 200 mg L-1 but excellent fungicidal activities against six fungus at 50 mg L-1, which were better than the control.展开更多
Metallene has been widely considered as an advanced electrocatalytic material due to its large specific surface area and highly active reaction sites.Herein,we design and synthesize ultrathin rhodium metallene(Rh ML)w...Metallene has been widely considered as an advanced electrocatalytic material due to its large specific surface area and highly active reaction sites.Herein,we design and synthesize ultrathin rhodium metallene(Rh ML)with abundant wrinkles to supply surface-strained Rh sites for driving acetonitrile electroreduction to ethylamine(AER).The electrochemical tests indicate that Rh ML shows an ethylamine yield rate of 137.1 mmol gcat^(-1) h^(-1) in an acidic solution,with stability lasting up to 200 h.Theoretical calculations reveal that Rh ML with wrinkle-induced compressive strain not only shows a lower energy barrier in the rate-determining step but also facilitates the ethylamine desorption process compared to wrinkle-free Rh ML and commercial Rh black.The assembled electrolyzer with bifunctional Rh ML shows an electrolysis voltage of 0.41 V at 10 mA cm^(-2),enabling simultaneous ethylamine production and hydrazine waste treatment.Furthermore,the voltage of an assembled hybrid zinc-acetonitrile battery can effectively drive this electrolyzer to achieve the dual AER process.This study provides guidance for improving the catalytic efficiency of surface atoms in two-dimensional materials,as well as the electrochemical synthesis technology for series-connected battery-electrolyzer systems.展开更多
The hydrazine oxidation reaction(HzOR)has garnered significant attention as a feasible approach to replace sluggish anodic reactions to save energy.Nevertheless,there are still difficulties in developing highly effici...The hydrazine oxidation reaction(HzOR)has garnered significant attention as a feasible approach to replace sluggish anodic reactions to save energy.Nevertheless,there are still difficulties in developing highly efficient catalysts for the HzOR.Herein,we report amorphous ruthenium nanosheets(a-Ru NSs)with a thickness of approximately 9.6 nm.As a superior bifunctional electrocatalyst,a-Ru NSs exhibited enhanced electrocatalytic performance toward both the HzOR and hydrogen evolution reaction(HER),outperforming benchmark Pt/C catalysts,where the a-Ru NSs achieved a work-ing potential of merely-76 mV and a low overpotential of only 17 mV to attain a current density of 10 mA·cm^(-2) for the HzOR and HER,respectively.Furthermore,a-Ru NSs displayed a low cell voltage of 28 mV at 10 mA·cm^(-2) for overall hy-drazine splitting in a two-electrode electrolyzer.In situ Raman spectra revealed that the a-Ru NSs can efficiently promote N‒N bond cleavage,thereby producing more*NH_(2)and accelerating the progress of the reaction.展开更多
In the field of Raman spectroscopy detection,the quest for a non–noble metal,recyclable,and highly sensitive detection substrate is of utmost importance.In this work,a new crystalline and noble metal–free substrate ...In the field of Raman spectroscopy detection,the quest for a non–noble metal,recyclable,and highly sensitive detection substrate is of utmost importance.In this work,a new crystalline and noble metal–free substrate of[Bi(DMF)_(8)][PMo_(12)O_(40)](Bi–PMo_(12))is designed,which is composed of[PMo_(12)O_(40)]^(3−)and solvated[Bi(DMF)_(8)]^(3+)cations.Mechanistic studies have revealed that Raman scattering quenching phenomenon arises from two main factors.Firstly,it arises from the absorption of the scattered light due to the transition of a single electron in the reduced state of MoV between 4d orbitals.Secondly,after the interaction between the substrate and hydrazine,the surface undergoes varying degrees of roughening,leading to an impact on the scattered light intensity.These two effects collectively contribute to the detection of low concentrations of N_(2)H_(4).As a result,Bi–PMo_(12)opens up a novel Raman scattering quenching mechanism to realize the detection of reduced N_(2)H_(4)small molecules.A remarkably low detection limit of 4.5×10^(−9)ppm for N_(2)H_(4)is achieved on the Bi–PMo_(12)substrate.This detection has a lower concentration than the currently known SERS detection of N_(2)H_(4).Moreover,Bi–PMo_(12)can be recovered and reused through recrystallization,achieving a recovery rate of up to ca.51%.This study reveals the underlying potential of crystalline polyoxometalate materials in the field of Raman detection,thus opening up new avenues for highly sensitive analysis using Raman techniques.展开更多
Hydrazine-assisted water electrolysis presents a promising and efficient hydrogen production technology.However,developing high-performance hydrazine oxidation reaction(HzOR)and hydrogen evolution reaction(HER)bifunct...Hydrazine-assisted water electrolysis presents a promising and efficient hydrogen production technology.However,developing high-performance hydrazine oxidation reaction(HzOR)and hydrogen evolution reaction(HER)bifunctional catalysts remains challenging.Here,we report a bifunctional electrocatalyst of Ru NCs@NPC,embedding the ultrafine Ru nanoclusters into N-doped porous carbon via microwave reduction.Due to the ultrafine Ru nanoclusters and N doping,the composite exhibits exceptional activity for both HER and HzOR,requiring−55 and−67 mV to reach 10 mA·cm^(−2) in alkaline media.In the overall hydrazine splitting(OHzS)system,Ru NCs@NPC is used as both anode and cathode materials,achieving 10 mA·cm^(−2) only at 0.036 V.The zinc hydrazine(Zn-Hz)battery assembled with Ru NCs@NPC cathode and Zn foil anode can provide a stable voltage of 0.4 V and exhibit 98.5%energy efficiency.Therefore,integrating Zn-Hz battery with OHzS system enables self-powered H_(2) evolution.The density function theory calculations reveal that the Ru-N bond increases the metal-support interaction.展开更多
Sustainable H_(2) production based on hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR) has attracted wide attention due to minimal energy consumption compared to overall water electrolysis.The...Sustainable H_(2) production based on hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR) has attracted wide attention due to minimal energy consumption compared to overall water electrolysis.The present study focuses on the design and construction of heterostructured CoPB@NiFe-OH applied as efficient bifunctional catalysts to sustainably produce hydrogen and remove hydrazine in alkaline media.Impressively,CoPB@NiFe-OH heterointerface exhibits an HzOR potential of-135 mV at the current density of 10 mA cm^(2) when the P to B atom ratio was 0.2,simultaneously an HER potential of-32 mV toward HER when the atom ratio of P and B was 0.5.Thus,hydrogen production without an outer voltage accompanied by a small current density output of 25 mA cm^(2) is achieved,surpassing most reported catalysts.In addition,DFT calculations demonstrate the Co sites in CoPB upgrades H*adsorption,while the Ni sites in NiFe-OH optimizes the adsorption energy of N_(2)H_(4)*due to electron transfer from CoPB to NiFe-OH at the heterointerface,ultimately leading to exceptional performance in hydrazine-assistant water electrolysis via HER coupled with HzOR.展开更多
Controllable hydrogen production via the catalytic decomposition of hydrous hydrazine(N_(2)H_(4)·H_(2)O)holds significant promise for mobile and portable applications.However,current catalysts suffer from unsatis...Controllable hydrogen production via the catalytic decomposition of hydrous hydrazine(N_(2)H_(4)·H_(2)O)holds significant promise for mobile and portable applications.However,current catalysts suffer from unsatisfactory reaction activity and hydrogen(H2)selectivity.Based on the unique redox properties of CeO_(2),this article aims to enhance the thermal catalytic performance for the decomposition of N_(2)H_(4)·H_(2)O by improving metal-support interactions between the TiCeO_(2)and NiPt active components.Meanwhile,the sea urchin-like TiCeO_(2)support,which is more conducive to the dispersion of the NiPt nanoparticles and provides more reactive sites for the reaction,was used to immobilize Ni-Pt into the NixPt1-x/TiCeO_(2)sample using the impregnation-reduction method.By modulating Ce doping and the Ni-Pt molar ratio,samples with different Ni-Pt compositions were synthesized.The optimal Ni0.5Pt0.5/TiCeO_(2)(nNi:nPt=1)shows the highest catalytic performance compared with the other samples,with a TOF(turnover frequency)of 212.58 min-1and 100%hydrogen selectivity at 323 K.Furthermore,the hydrogen selectivity remains 100%after six cycles.This remarkable activity and stability provide valuable insights and encouragement for accelerating the practical application of N_(2)H_(4)·H_(2)O as a viable hydrogen carrier.展开更多
Chemical hydrogen storage technology is crucial for the widespread use of hydrogen,with significant research progress being made in hydrazine hydrate(N_(2)H_(4)·H_(2)O).However,the efficient decomposition of N_(2...Chemical hydrogen storage technology is crucial for the widespread use of hydrogen,with significant research progress being made in hydrazine hydrate(N_(2)H_(4)·H_(2)O).However,the efficient decomposition of N_(2)H_(4)·H_(2)O remains a major challenge,hindered by dynamic constraints.To address this,we prepared NiPt nanoparticles deposited onto urchin-like TiO_(2)(u-TiO_(2))using the impregnation-reduction method,resulting in the NiPt/u-TiO_(2)catalyst.Remarkably,the Ni0.5Pt0.5/u-TiO_(2)catalyst demonstrated 100%H_(2)selectivity,ultrahigh catalytic activity and remarkable durability for N_(2)H_(4)·H_(2)O dehydrogenation,with a turnover frequency(TOF)of115.8 min^(-1),surpassing that of the corresponding NiPt/commercial TiO_(2)(c-TiO_(2)).Characterization and experimental findings suggest that the remarkable activity may originate from the unique urchin-like structure of the catalyst,along with the synergistic interaction between NiPt metals and the support.This research opens new avenues for designing nanomaterials with morphology advantages for hydrogen evolution reaction.展开更多
Hydrogen peroxide(H_(2)O_(2))production via electrochemical two-electron oxygen reduction reaction(ORR)holds a great promise for sustainable energy storage.However,the issues such as high energy consumption and diffic...Hydrogen peroxide(H_(2)O_(2))production via electrochemical two-electron oxygen reduction reaction(ORR)holds a great promise for sustainable energy storage.However,the issues such as high energy consumption and difficult extraction of thermodynamically unstable H_(2)O_(2) still need to be resolved.Herein,we reported a unified system for energy-out production and downstream conversion of H_(2)O_(2).By replacing the sluggish oxygen evolution reaction with a hydrazine oxidation reaction(HzOR),the cell of twoelectron ORR coupled with HzOR achieves the co-generation of electricity energy and valuable H_(2)O_(2).By employing Ru single atoms anchored on cobalt hydroxide(for HzOR)and NiSe_(2)(for ORR)as electrocatalysts,both exhibiting onset potentials near the theoretical values for their respective reactions,the ORR‖HzOR cell exhibits an energy output of 3.58 mW cm^(-2) and generates 0.66 kWh of electricity per kg of H_(2)O_(2).with a production rate of 583 mmol h^(-1) H_(2)O_(2).The produced H_(2)O_(2) was subsequently in-situ upgraded via three downstream conversion pathways to yield value-added products of sodium percarbonate,sodium peroxyborate,and ethylene glycol.A techno-economic analysis confirmed the economic viability of this ORR‖HzOR coupled with downstream conversion system.展开更多
Zn-CO_(2)batteries(ZCBs)are promising for CO_(2)conversion and electric energy release.However,the ZCBs couple the electrochemical CO_(2)reduction(ECO_(2)R)with the oxygen evolution reaction and competitive hydrogen e...Zn-CO_(2)batteries(ZCBs)are promising for CO_(2)conversion and electric energy release.However,the ZCBs couple the electrochemical CO_(2)reduction(ECO_(2)R)with the oxygen evolution reaction and competitive hydrogen evolution reaction,which normally causes ultrahigh charge voltage and CO_(2)conversion efficiency attenuation,thereby resulting in~90%total power consumption.Herein,isolated FeN_(3)sites encapsulated in hierarchical porous carbon nanoboxes(Fe-HPCN,derived from the thermal activation process of ferrocene and polydopamine-coated cubic ZIF-8)were proposed for hydrazine-assisted rechargeable ZCBs based on ECO_(2)R(discharging process:CO_(2)+2H+→CO+H_(2)O)and hydrazine oxidation reaction(HzOR,charging process:N_(2)H_(4)+4OH−→N_(2)+4H_(2)O+4e^(−)).The isolated FeN_(3)endows the HzOR with a lower overpotential and boosts the ECO_(2)R with a 96%CO Faraday efficiency(FECO).Benefitting from the bifunctional ECO_(2)R and HzOR catalytic activities,the homemade hydrazine-assisted rechargeable ZCBs assembled with the Fe-HPCN air cathode exhibited an ultralow charge voltage(decreasing by~1.84 V),excellent CO selectivity(FECO close to 100%),and high 89%energy efficiency.In situ infrared spectroscopy confirmed that Fe-HPCN can generate rate-determining*N_(2)and*CO intermediates during HzOR and ECO_(2)R.This paper proposes FeN_(3)centers for bifunctional ECO_(2)R/HzOR performance and further presents the pioneering achievements of ECO_(2)R and HzOR for hydrazine-assisted rechargeable ZCBs.展开更多
Zinc neutral leaching residue（ZNLR） from hydrometallurgical zinc smelting processing can be determined as hazardous intermediate containing considerable amounts of Cd and Zn which have great threats to the environme...Zinc neutral leaching residue（ZNLR） from hydrometallurgical zinc smelting processing can be determined as hazardous intermediate containing considerable amounts of Cd and Zn which have great threats to the environment. The ZNLR contained approximately 35.99% Zn, 15.93% Fe and 0.26% Cd, and Cd mainly existed as ferrites in the ZNLR in this research. Reductive acid leaching of ZNLR was investigated. The effects of hydrazine sulfate concentration, initial sulfuric acid concentration, temperature, duration and liquid-to-solid ratio on the extraction of Cd, Zn and Fe were examined. The extraction efficiencies of Cd, Zn and Fe reached 90.81%, 95.83% and 94.19%, respectively when the leaching parameters were fixed as follows： hydrazine sulfate concentration, 33.3 g/L; sulfuric acid concentration, 80 g/L; temperature, 95 °C; duration of leaching, 120 min; liquid-to-solid ratio, 10 m L/g and agitation, 400 r/min. XRD and SEM-EDS analyses of the leaching residue confirmed that lead sulfate（Pb SO4） and hydrazinium zinc sulfate（（N2H5）2Zn（SO4）2） were the main phases remaining in the reductive leaching residue.展开更多
This paper focused on investigating high-efficient reductants of recovering selenium and tellurium from degoldizedsolution of copper anode slimes.Firstly,the effect of various reductants on recovery rates of Se and Te...This paper focused on investigating high-efficient reductants of recovering selenium and tellurium from degoldizedsolution of copper anode slimes.Firstly,the effect of various reductants on recovery rates of Se and Te was investigated based onthermodynamic analysis of various metallic ions in degoldized solution.Secondly,the single factor experiments were made toinvestigate the effect of the process parameters on recovering Se and Te with hydrazine hydrate.Finally,the hydroxylaminehydrochloride was added to intensify the extraction efficiencies of Se and Te.The results indicated that hydrazine hydrate was themost suitable reductant,and the recovery rates of Se and Te are71.23%and76.50%,respectively;the recovery rates of Se and Tewere92.07%and97.81%,respectively,under the optimal process conditions of hydrazine hydrate dosage of0.2133mol/L,H+concentration of4.305mol/L,reaction temperature of85°C and reaction time of5h;the recovery rate of Se was97.59%,and that Tereached up to100%when hydroxylamine hydrochloride dosage was1.5116mol/L.展开更多
Hydrazine sulfate was used as a reducing agent for the leaching of Li,Ni,Co and Mn from spent lithium-ion batteries.The effects of the reaction conditions on the leaching mechanism and kinetics were characterized and ...Hydrazine sulfate was used as a reducing agent for the leaching of Li,Ni,Co and Mn from spent lithium-ion batteries.The effects of the reaction conditions on the leaching mechanism and kinetics were characterized and examined.97%of the available Li,96%of the available Ni,95%of the available Co,and 86%of the available Mn are extracted under the following optimized conditions:sulfuric acid concentration of 2.0 mol/L,hydrazine sulfate dosage of 30 g/L,solid-to-liquid ratio of 50 g/L,temperature of 80℃,and leaching time of 60 min.The activation energies of the leaching are determined to be 44.32,59.37 and 55.62 k J/mol for Li,Ni and Co,respectively.By performing X-ray diffraction and scanning electron microscopy in conjunction with energy dispersive X-ray spectroscopy,it is confirmed that the main phase in the leaching residue is MnO2.The results show that hydrazine sulfate is an effective reducing agent in the acid leaching process for spent lithium-ion batteries.展开更多
Searching for highly efficient catalysts toward dehydrogenation of hydrazine for chemical hydrogen storage is highly desirable for the development of hydrogen economy. Herein, we report a simple in situ co-reduction s...Searching for highly efficient catalysts toward dehydrogenation of hydrazine for chemical hydrogen storage is highly desirable for the development of hydrogen economy. Herein, we report a simple in situ co-reduction synthesis of NiPt nanoparticles supported on CeO_2 nanospheres and their superior catalytic performance for hydrogen generation from alkaline solution of hydrazine at room temperature. Thanks to the strong electronic interaction arising from synergistic effect at atomic lever and support-metal interaction between NiPt and CeO_2.The obtained Ni_5Pt_5-CeO_2 catalyst exhibits 100% hydrogen selectivity and superior catalytic performance for hydrogen generation from alkaline solution of hydrazine at room temperature, with a TOF value of 416 h 1.展开更多
The current study describes the application of a new extraction method for efficient uranium adsorption via cost-effective hydrazine-impregnated activated carbon.Various experimental parameters such as time, adsorbent...The current study describes the application of a new extraction method for efficient uranium adsorption via cost-effective hydrazine-impregnated activated carbon.Various experimental parameters such as time, adsorbent weight, temperature(°C), and uranium concentration were thoroughly investigated. The synthesized adsorbent was characterized via X-ray diffraction, Fourier transformation infrared spectroscopy(FT-IR), scanning electron microscopy, and thermogravimetric analysis. The results showed86% uranium extraction under optimized conditions(20% P2O5 at 25 °C, 120 min). The obtained findings fit well with thermodynamic and isothermal(Langmuir and Freundlich isotherms) models and pseudo second-order kinetics. In thermodynamic studies, the negative sign of(DG°) specified the spontaneity of process, the negative sign of(DH°) revealed endothermicity, and the positive sign of(DS°) showed high randomness after adsorption.展开更多
Hydrazine-assisted water electrolysis is a promising energy conversion technology for highly efficient hydrogen production.Rational design of bifunctional electrocatalysts,which can simultaneously accelerate hydrogen ...Hydrazine-assisted water electrolysis is a promising energy conversion technology for highly efficient hydrogen production.Rational design of bifunctional electrocatalysts,which can simultaneously accelerate hydrogen evolution reaction(HER)/hydrazine oxidation reaction(HzOR)kinetics,is the key step.Herein,we demonstrate the development of ultrathin P/Fe co-doped NiSe_(2) nanosheets supported on modified Ni foam(P/Fe-NiSe_(2)) synthesized through a facile electrodeposition process and subsequent heat treatment.Based on electrochemical measurements,characterizations,and density functional theory calculations,a favorable“2+2”reaction mechanism with a two-step HER process and a two-step HzOR step was fully proved and the specific effect of P doping on HzOR kinetics was investigated.P/Fe-NiSe_(2) thus yields an impressive electrocatalytic performance,delivering a high current density of 100 mA cm^(−2) with potentials of−168 and 200 mV for HER and HzOR,respectively.Additionally,P/Fe-NiSe_(2) can work efficiently for hydrazine-assisted water electrolysis and Zn-Hydrazine(Zn-Hz)battery,making it promising for practical application.展开更多
In this study, a resorufin derivative RTP-1, which is a novel fluorescent ‘‘turn-on＇＇ probe for sensitive detection of hydrazine within 30 min, is designed and synthesized. The selective deprotection of the ester ...In this study, a resorufin derivative RTP-1, which is a novel fluorescent ‘‘turn-on＇＇ probe for sensitive detection of hydrazine within 30 min, is designed and synthesized. The selective deprotection of the ester group of the probe by hydrazine led to a prominent enhancement of fluorescent intensity, as well as a remarkable color change from colorless to pink, which could be distinguished by naked eye. The fluorescence enhancement showed decent linear relationship with hydrazine concentration ranging from 0 to 50 mmol/L, with a detection limit of 0.84 mmol/L. The specificity of RTP-1 for hydrazine to a number of metal ions, anions and amines is satisfactory. The sensing mechanism of RTP-1 and hydrazine was evaluated by HPLC, ESI mass spectrometry and density functional theory（DFT）.Moreover, we have utilized this fluorescent probe for imaging hydrazine in living cells, and the fluorescence was clearly observed when the cells were incubated with hydrazine（100 mmol/L） for 30 min.展开更多
One-dimensional Ni nanostructures were synthesized via a hydrazine reduction route under external magnetic fields. The mixture of de-ionized water and ethanol was used as the reaction solvent and hydrazine hydrate as ...One-dimensional Ni nanostructures were synthesized via a hydrazine reduction route under external magnetic fields. The mixture of de-ionized water and ethanol was used as the reaction solvent and hydrazine hydrate as reducing agents. The morphology and properties of Ni nanostructures were characterized by X-ray diffractometer(XRD), scanning electron microscopy(SEM), and vibrating sample magnetometer(VSM). It was found that the magnetic field strength, concentration of Ni ions,reaction time and temperature as well as p H values played key roles on formation, microstructures and magnetic properties of Ni nanowires. The optimal wires have diameter of ~200 nm and length up to ~200 μm. And their coercivity is ~260 Oe, which is much larger than the commercial Ni powders of 31 Oe. This work presents a simple, low-cost, environment-friendly and large-scale production approach to fabricate one-dimensional magnetic materials. The resulting materials may have potential applications in conductive filters, magnetic sensors and catalytic agents.展开更多
Aluminium hydroxide precipitation from synthetic sodium aluminate solution was studied in the presence of hydrazine or hydrogen peroxide. The addition of low concentration of hydrazine is found to be effective, while ...Aluminium hydroxide precipitation from synthetic sodium aluminate solution was studied in the presence of hydrazine or hydrogen peroxide. The addition of low concentration of hydrazine is found to be effective, while higher amount of hydrogen peroxide is required to generate similar effect. XRD data confirm the product phase to be gibbsitic by nature. The scanning electron micrographs （SEM） show that agglomerated products form in the presence of hydrazine while fine discrete particles are produced with hydrogen peroxide. The probable mechanism of precipitation in the presence of hydrazine and hydrogen peroxide is also discussed.展开更多
文摘In search of environmentally benign compounds with high biological activity, low toxicity and low resistance, 8 novel benzoyl hydrazines containing pyrazole were designed and synthesized. All compounds were characterized by I H NMR spectra and HRMS. The preliminary results of biological activity assessment indicated that most of title compounds exhibited certain insecticidal activities against M）,thimna separata Walker at 200 mg L-1 but excellent fungicidal activities against six fungus at 50 mg L-1, which were better than the control.
基金supported by the National Natural Science Foundation of China(22272103)the National Natural Science Foundation of China for the Youth(22309108,22202076)+3 种基金the Science and Technology Innovation Team of Shaanxi Province(2023-CX-TD-27)the China Postdoctoral Science Foundation(2023TQ0204)the Young Scientist Initiative Project of School of Materials Science and Engineering at Shaanxi Normal University(2024YSIP-MSE-SNNU008)Sanqin Scholars Innovation Teams in Shaanxi Province in China.
文摘Metallene has been widely considered as an advanced electrocatalytic material due to its large specific surface area and highly active reaction sites.Herein,we design and synthesize ultrathin rhodium metallene(Rh ML)with abundant wrinkles to supply surface-strained Rh sites for driving acetonitrile electroreduction to ethylamine(AER).The electrochemical tests indicate that Rh ML shows an ethylamine yield rate of 137.1 mmol gcat^(-1) h^(-1) in an acidic solution,with stability lasting up to 200 h.Theoretical calculations reveal that Rh ML with wrinkle-induced compressive strain not only shows a lower energy barrier in the rate-determining step but also facilitates the ethylamine desorption process compared to wrinkle-free Rh ML and commercial Rh black.The assembled electrolyzer with bifunctional Rh ML shows an electrolysis voltage of 0.41 V at 10 mA cm^(-2),enabling simultaneous ethylamine production and hydrazine waste treatment.Furthermore,the voltage of an assembled hybrid zinc-acetonitrile battery can effectively drive this electrolyzer to achieve the dual AER process.This study provides guidance for improving the catalytic efficiency of surface atoms in two-dimensional materials,as well as the electrochemical synthesis technology for series-connected battery-electrolyzer systems.
基金supported by the National Key R&D Program of China(2018YFA0702001)National Natural Science Foundation of China(22371268,22301287)+3 种基金Fundamental Research Funds for the Central Universities(WK2060000016)Anhui Provincial Natural Science Foundation(2208085J09,2208085QB33)Collaborative Innovation Program of Hefei Science Center,CAS(2022HSC-CIP020)Youth Innovation Promotion Association of the Chinese Academy of Science(2018494)and USTC Tang Scholar.
文摘The hydrazine oxidation reaction(HzOR)has garnered significant attention as a feasible approach to replace sluggish anodic reactions to save energy.Nevertheless,there are still difficulties in developing highly efficient catalysts for the HzOR.Herein,we report amorphous ruthenium nanosheets(a-Ru NSs)with a thickness of approximately 9.6 nm.As a superior bifunctional electrocatalyst,a-Ru NSs exhibited enhanced electrocatalytic performance toward both the HzOR and hydrogen evolution reaction(HER),outperforming benchmark Pt/C catalysts,where the a-Ru NSs achieved a work-ing potential of merely-76 mV and a low overpotential of only 17 mV to attain a current density of 10 mA·cm^(-2) for the HzOR and HER,respectively.Furthermore,a-Ru NSs displayed a low cell voltage of 28 mV at 10 mA·cm^(-2) for overall hy-drazine splitting in a two-electrode electrolyzer.In situ Raman spectra revealed that the a-Ru NSs can efficiently promote N‒N bond cleavage,thereby producing more*NH_(2)and accelerating the progress of the reaction.
基金the financial support from the National Natural Science Foundation of China(No.21971085)the Natural Science Foundation of Shandong Province(No.ZR2021MB008)。
文摘In the field of Raman spectroscopy detection,the quest for a non–noble metal,recyclable,and highly sensitive detection substrate is of utmost importance.In this work,a new crystalline and noble metal–free substrate of[Bi(DMF)_(8)][PMo_(12)O_(40)](Bi–PMo_(12))is designed,which is composed of[PMo_(12)O_(40)]^(3−)and solvated[Bi(DMF)_(8)]^(3+)cations.Mechanistic studies have revealed that Raman scattering quenching phenomenon arises from two main factors.Firstly,it arises from the absorption of the scattered light due to the transition of a single electron in the reduced state of MoV between 4d orbitals.Secondly,after the interaction between the substrate and hydrazine,the surface undergoes varying degrees of roughening,leading to an impact on the scattered light intensity.These two effects collectively contribute to the detection of low concentrations of N_(2)H_(4).As a result,Bi–PMo_(12)opens up a novel Raman scattering quenching mechanism to realize the detection of reduced N_(2)H_(4)small molecules.A remarkably low detection limit of 4.5×10^(−9)ppm for N_(2)H_(4)is achieved on the Bi–PMo_(12)substrate.This detection has a lower concentration than the currently known SERS detection of N_(2)H_(4).Moreover,Bi–PMo_(12)can be recovered and reused through recrystallization,achieving a recovery rate of up to ca.51%.This study reveals the underlying potential of crystalline polyoxometalate materials in the field of Raman detection,thus opening up new avenues for highly sensitive analysis using Raman techniques.
基金supported by the National Natural Science Foundation of China(Nos.52371222 and 52271211)the Natural Science Foundation of Hunan Province in China(Nos.2024JJ4022,2023JJ30277 and 2023JJ50043)+1 种基金the Science and Technology Innovation Program of Hunan Province(No.2023RC3185),ChinaHORIZON-Marie Skłodowska-Curie Actions-2021-PF(No.101065098),European Union.
文摘Hydrazine-assisted water electrolysis presents a promising and efficient hydrogen production technology.However,developing high-performance hydrazine oxidation reaction(HzOR)and hydrogen evolution reaction(HER)bifunctional catalysts remains challenging.Here,we report a bifunctional electrocatalyst of Ru NCs@NPC,embedding the ultrafine Ru nanoclusters into N-doped porous carbon via microwave reduction.Due to the ultrafine Ru nanoclusters and N doping,the composite exhibits exceptional activity for both HER and HzOR,requiring−55 and−67 mV to reach 10 mA·cm^(−2) in alkaline media.In the overall hydrazine splitting(OHzS)system,Ru NCs@NPC is used as both anode and cathode materials,achieving 10 mA·cm^(−2) only at 0.036 V.The zinc hydrazine(Zn-Hz)battery assembled with Ru NCs@NPC cathode and Zn foil anode can provide a stable voltage of 0.4 V and exhibit 98.5%energy efficiency.Therefore,integrating Zn-Hz battery with OHzS system enables self-powered H_(2) evolution.The density function theory calculations reveal that the Ru-N bond increases the metal-support interaction.
基金the Department of Science and Technology of Anhui Province(2022h11020024)Anhui Construction Engineering Group Co.,Ltd.(SG2025Q11)+4 种基金Basic Research Project from Institute of Coal Chemistry,CAS(SCJC-HN-2022-17)Shanxi Province Science Foundation(20210302124446202102070301018)The University Synergy Innovation Program of Anhui Province(GXXT-2022-27)Scientific Research Foundation for High-level Talents of Anhui University of Science and Technology(2023yjrc51)for funding。
文摘Sustainable H_(2) production based on hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR) has attracted wide attention due to minimal energy consumption compared to overall water electrolysis.The present study focuses on the design and construction of heterostructured CoPB@NiFe-OH applied as efficient bifunctional catalysts to sustainably produce hydrogen and remove hydrazine in alkaline media.Impressively,CoPB@NiFe-OH heterointerface exhibits an HzOR potential of-135 mV at the current density of 10 mA cm^(2) when the P to B atom ratio was 0.2,simultaneously an HER potential of-32 mV toward HER when the atom ratio of P and B was 0.5.Thus,hydrogen production without an outer voltage accompanied by a small current density output of 25 mA cm^(2) is achieved,surpassing most reported catalysts.In addition,DFT calculations demonstrate the Co sites in CoPB upgrades H*adsorption,while the Ni sites in NiFe-OH optimizes the adsorption energy of N_(2)H_(4)*due to electron transfer from CoPB to NiFe-OH at the heterointerface,ultimately leading to exceptional performance in hydrazine-assistant water electrolysis via HER coupled with HzOR.
基金Project supported by the National Natural Science Foundation of China(22478001,22108238,22108002,U22A20408)Excellent Young Scholars Program of Natural Science Foundation Anhui Province(2408085Y005)+2 种基金Excellent Youth Scholars Program of Higher Education Institutions of Anhui Province(2024AH030008)the Open Fund of Shanghai Jiao Tong University Shaoxing Research Institute(JDSX2023014)the Outstanding Scientific Research and Innovation Team Program of Higher Education Institutions of Anhui Province(2023AH010015)。
文摘Controllable hydrogen production via the catalytic decomposition of hydrous hydrazine(N_(2)H_(4)·H_(2)O)holds significant promise for mobile and portable applications.However,current catalysts suffer from unsatisfactory reaction activity and hydrogen(H2)selectivity.Based on the unique redox properties of CeO_(2),this article aims to enhance the thermal catalytic performance for the decomposition of N_(2)H_(4)·H_(2)O by improving metal-support interactions between the TiCeO_(2)and NiPt active components.Meanwhile,the sea urchin-like TiCeO_(2)support,which is more conducive to the dispersion of the NiPt nanoparticles and provides more reactive sites for the reaction,was used to immobilize Ni-Pt into the NixPt1-x/TiCeO_(2)sample using the impregnation-reduction method.By modulating Ce doping and the Ni-Pt molar ratio,samples with different Ni-Pt compositions were synthesized.The optimal Ni0.5Pt0.5/TiCeO_(2)(nNi:nPt=1)shows the highest catalytic performance compared with the other samples,with a TOF(turnover frequency)of 212.58 min-1and 100%hydrogen selectivity at 323 K.Furthermore,the hydrogen selectivity remains 100%after six cycles.This remarkable activity and stability provide valuable insights and encouragement for accelerating the practical application of N_(2)H_(4)·H_(2)O as a viable hydrogen carrier.
基金financially supported by the National Natural Science Foundation of China(Nos.22478001,U22A20408 and 22108238)the Excellent Young Scholars Program of Natural Science Foundation Anhui Province(No.2408085Y005)+3 种基金the Excellent Youth Scholars Program of Higher Education Institutions of Anhui Province(No.2024AH030008)the Open Fund of Shanghai Jiao Tong University Shaoxing Research Institute(No.JDSX2023014)the State Key Laboratory of Clean Energy Utilization(No.ZJUCEU2024017)the Outstanding Scientific Research and Innovation Team Program of Higher Education Institutions of Anhui Province(No.2023AH010015)
文摘Chemical hydrogen storage technology is crucial for the widespread use of hydrogen,with significant research progress being made in hydrazine hydrate(N_(2)H_(4)·H_(2)O).However,the efficient decomposition of N_(2)H_(4)·H_(2)O remains a major challenge,hindered by dynamic constraints.To address this,we prepared NiPt nanoparticles deposited onto urchin-like TiO_(2)(u-TiO_(2))using the impregnation-reduction method,resulting in the NiPt/u-TiO_(2)catalyst.Remarkably,the Ni0.5Pt0.5/u-TiO_(2)catalyst demonstrated 100%H_(2)selectivity,ultrahigh catalytic activity and remarkable durability for N_(2)H_(4)·H_(2)O dehydrogenation,with a turnover frequency(TOF)of115.8 min^(-1),surpassing that of the corresponding NiPt/commercial TiO_(2)(c-TiO_(2)).Characterization and experimental findings suggest that the remarkable activity may originate from the unique urchin-like structure of the catalyst,along with the synergistic interaction between NiPt metals and the support.This research opens new avenues for designing nanomaterials with morphology advantages for hydrogen evolution reaction.
基金the National Natural Science Foundation of China(U21A20286 to Y.H.,22206054 to Y.H.,and 22478310 to J.Z.)the Fundamental Research Funds for the Central China Normal University(CCNU)。
文摘Hydrogen peroxide(H_(2)O_(2))production via electrochemical two-electron oxygen reduction reaction(ORR)holds a great promise for sustainable energy storage.However,the issues such as high energy consumption and difficult extraction of thermodynamically unstable H_(2)O_(2) still need to be resolved.Herein,we reported a unified system for energy-out production and downstream conversion of H_(2)O_(2).By replacing the sluggish oxygen evolution reaction with a hydrazine oxidation reaction(HzOR),the cell of twoelectron ORR coupled with HzOR achieves the co-generation of electricity energy and valuable H_(2)O_(2).By employing Ru single atoms anchored on cobalt hydroxide(for HzOR)and NiSe_(2)(for ORR)as electrocatalysts,both exhibiting onset potentials near the theoretical values for their respective reactions,the ORR‖HzOR cell exhibits an energy output of 3.58 mW cm^(-2) and generates 0.66 kWh of electricity per kg of H_(2)O_(2).with a production rate of 583 mmol h^(-1) H_(2)O_(2).The produced H_(2)O_(2) was subsequently in-situ upgraded via three downstream conversion pathways to yield value-added products of sodium percarbonate,sodium peroxyborate,and ethylene glycol.A techno-economic analysis confirmed the economic viability of this ORR‖HzOR coupled with downstream conversion system.
基金National Natural Science Foundation of China,Grant/Award Number:12274118Double First Class University Plan,Grant/Award Number:C176220100042+2 种基金National Natural Science Foundation of China-Yunnan Joint Fund,Grant/Award Number:U2002213Open Foundation of Guangxi Key Laboratory of Processing for Non-Ferrous Metals and Featured Materials,Grant/Award Number:2022GXYSOF10Henan Center for Outstanding Overseas Scientists,Grant/Award Number:GZS2023007.
文摘Zn-CO_(2)batteries(ZCBs)are promising for CO_(2)conversion and electric energy release.However,the ZCBs couple the electrochemical CO_(2)reduction(ECO_(2)R)with the oxygen evolution reaction and competitive hydrogen evolution reaction,which normally causes ultrahigh charge voltage and CO_(2)conversion efficiency attenuation,thereby resulting in~90%total power consumption.Herein,isolated FeN_(3)sites encapsulated in hierarchical porous carbon nanoboxes(Fe-HPCN,derived from the thermal activation process of ferrocene and polydopamine-coated cubic ZIF-8)were proposed for hydrazine-assisted rechargeable ZCBs based on ECO_(2)R(discharging process:CO_(2)+2H+→CO+H_(2)O)and hydrazine oxidation reaction(HzOR,charging process:N_(2)H_(4)+4OH−→N_(2)+4H_(2)O+4e^(−)).The isolated FeN_(3)endows the HzOR with a lower overpotential and boosts the ECO_(2)R with a 96%CO Faraday efficiency(FECO).Benefitting from the bifunctional ECO_(2)R and HzOR catalytic activities,the homemade hydrazine-assisted rechargeable ZCBs assembled with the Fe-HPCN air cathode exhibited an ultralow charge voltage(decreasing by~1.84 V),excellent CO selectivity(FECO close to 100%),and high 89%energy efficiency.In situ infrared spectroscopy confirmed that Fe-HPCN can generate rate-determining*N_(2)and*CO intermediates during HzOR and ECO_(2)R.This paper proposes FeN_(3)centers for bifunctional ECO_(2)R/HzOR performance and further presents the pioneering achievements of ECO_(2)R and HzOR for hydrazine-assisted rechargeable ZCBs.
基金Project(2012FJ1010)supported by the Key Project of Science and Technology of Hunan ProvinceChina+2 种基金Project(51474247)supported by the National Natural Science Foundation of ChinaProject(2012GS430201)supported by the Science and Technology Program for Public WellbeingChina
文摘Zinc neutral leaching residue（ZNLR） from hydrometallurgical zinc smelting processing can be determined as hazardous intermediate containing considerable amounts of Cd and Zn which have great threats to the environment. The ZNLR contained approximately 35.99% Zn, 15.93% Fe and 0.26% Cd, and Cd mainly existed as ferrites in the ZNLR in this research. Reductive acid leaching of ZNLR was investigated. The effects of hydrazine sulfate concentration, initial sulfuric acid concentration, temperature, duration and liquid-to-solid ratio on the extraction of Cd, Zn and Fe were examined. The extraction efficiencies of Cd, Zn and Fe reached 90.81%, 95.83% and 94.19%, respectively when the leaching parameters were fixed as follows： hydrazine sulfate concentration, 33.3 g/L; sulfuric acid concentration, 80 g/L; temperature, 95 °C; duration of leaching, 120 min; liquid-to-solid ratio, 10 m L/g and agitation, 400 r/min. XRD and SEM-EDS analyses of the leaching residue confirmed that lead sulfate（Pb SO4） and hydrazinium zinc sulfate（（N2H5）2Zn（SO4）2） were the main phases remaining in the reductive leaching residue.
基金Project(201407300993)supported by Xinjiang Autonomous Region Science and Technology Support Project,China
文摘This paper focused on investigating high-efficient reductants of recovering selenium and tellurium from degoldizedsolution of copper anode slimes.Firstly,the effect of various reductants on recovery rates of Se and Te was investigated based onthermodynamic analysis of various metallic ions in degoldized solution.Secondly,the single factor experiments were made toinvestigate the effect of the process parameters on recovering Se and Te with hydrazine hydrate.Finally,the hydroxylaminehydrochloride was added to intensify the extraction efficiencies of Se and Te.The results indicated that hydrazine hydrate was themost suitable reductant,and the recovery rates of Se and Te are71.23%and76.50%,respectively;the recovery rates of Se and Tewere92.07%and97.81%,respectively,under the optimal process conditions of hydrazine hydrate dosage of0.2133mol/L,H+concentration of4.305mol/L,reaction temperature of85°C and reaction time of5h;the recovery rate of Se was97.59%,and that Tereached up to100%when hydroxylamine hydrochloride dosage was1.5116mol/L.
基金Project(51674298)supported by the National Natural Science Foundation of ChinaProject supported by Anhui Province Research and Development Innovation Program,China。
文摘Hydrazine sulfate was used as a reducing agent for the leaching of Li,Ni,Co and Mn from spent lithium-ion batteries.The effects of the reaction conditions on the leaching mechanism and kinetics were characterized and examined.97%of the available Li,96%of the available Ni,95%of the available Co,and 86%of the available Mn are extracted under the following optimized conditions:sulfuric acid concentration of 2.0 mol/L,hydrazine sulfate dosage of 30 g/L,solid-to-liquid ratio of 50 g/L,temperature of 80℃,and leaching time of 60 min.The activation energies of the leaching are determined to be 44.32,59.37 and 55.62 k J/mol for Li,Ni and Co,respectively.By performing X-ray diffraction and scanning electron microscopy in conjunction with energy dispersive X-ray spectroscopy,it is confirmed that the main phase in the leaching residue is MnO2.The results show that hydrazine sulfate is an effective reducing agent in the acid leaching process for spent lithium-ion batteries.
基金financially supported by the National Natural Science Foundation of China (No. 21571145)Large-scale Instrument and Equipment Sharing Foundation of Wuhan University
文摘Searching for highly efficient catalysts toward dehydrogenation of hydrazine for chemical hydrogen storage is highly desirable for the development of hydrogen economy. Herein, we report a simple in situ co-reduction synthesis of NiPt nanoparticles supported on CeO_2 nanospheres and their superior catalytic performance for hydrogen generation from alkaline solution of hydrazine at room temperature. Thanks to the strong electronic interaction arising from synergistic effect at atomic lever and support-metal interaction between NiPt and CeO_2.The obtained Ni_5Pt_5-CeO_2 catalyst exhibits 100% hydrogen selectivity and superior catalytic performance for hydrogen generation from alkaline solution of hydrazine at room temperature, with a TOF value of 416 h 1.
文摘The current study describes the application of a new extraction method for efficient uranium adsorption via cost-effective hydrazine-impregnated activated carbon.Various experimental parameters such as time, adsorbent weight, temperature(°C), and uranium concentration were thoroughly investigated. The synthesized adsorbent was characterized via X-ray diffraction, Fourier transformation infrared spectroscopy(FT-IR), scanning electron microscopy, and thermogravimetric analysis. The results showed86% uranium extraction under optimized conditions(20% P2O5 at 25 °C, 120 min). The obtained findings fit well with thermodynamic and isothermal(Langmuir and Freundlich isotherms) models and pseudo second-order kinetics. In thermodynamic studies, the negative sign of(DG°) specified the spontaneity of process, the negative sign of(DH°) revealed endothermicity, and the positive sign of(DS°) showed high randomness after adsorption.
基金supported by the National Natural Science Foundation of China(22179065,22111530112,21875118)the Tianjin Graduate Research and Innovation Project(2022BKY018)the Ph.D.Candidate Research Innovation Fund of NKU School of Materials Science and Engineering.
文摘Hydrazine-assisted water electrolysis is a promising energy conversion technology for highly efficient hydrogen production.Rational design of bifunctional electrocatalysts,which can simultaneously accelerate hydrogen evolution reaction(HER)/hydrazine oxidation reaction(HzOR)kinetics,is the key step.Herein,we demonstrate the development of ultrathin P/Fe co-doped NiSe_(2) nanosheets supported on modified Ni foam(P/Fe-NiSe_(2)) synthesized through a facile electrodeposition process and subsequent heat treatment.Based on electrochemical measurements,characterizations,and density functional theory calculations,a favorable“2+2”reaction mechanism with a two-step HER process and a two-step HzOR step was fully proved and the specific effect of P doping on HzOR kinetics was investigated.P/Fe-NiSe_(2) thus yields an impressive electrocatalytic performance,delivering a high current density of 100 mA cm^(−2) with potentials of−168 and 200 mV for HER and HzOR,respectively.Additionally,P/Fe-NiSe_(2) can work efficiently for hydrazine-assisted water electrolysis and Zn-Hydrazine(Zn-Hz)battery,making it promising for practical application.
基金supported by the National Basic Research Program of China (973 Program, Nos. 2012CB720600, 2012CB720603)the National Science Foundation of China (Nos. 91413109, 21202126)East Lake High-tech Zone 3551 Talents Scheme
文摘In this study, a resorufin derivative RTP-1, which is a novel fluorescent ‘‘turn-on＇＇ probe for sensitive detection of hydrazine within 30 min, is designed and synthesized. The selective deprotection of the ester group of the probe by hydrazine led to a prominent enhancement of fluorescent intensity, as well as a remarkable color change from colorless to pink, which could be distinguished by naked eye. The fluorescence enhancement showed decent linear relationship with hydrazine concentration ranging from 0 to 50 mmol/L, with a detection limit of 0.84 mmol/L. The specificity of RTP-1 for hydrazine to a number of metal ions, anions and amines is satisfactory. The sensing mechanism of RTP-1 and hydrazine was evaluated by HPLC, ESI mass spectrometry and density functional theory（DFT）.Moreover, we have utilized this fluorescent probe for imaging hydrazine in living cells, and the fluorescence was clearly observed when the cells were incubated with hydrazine（100 mmol/L） for 30 min.
基金support of the National Basic Research Program of China(No.2006CB300406)Shanghai Science and Technology Grant(No:0752nm015)+2 种基金National Natural Science Foundation of China(No.50730008,20504021)Natural Science Foundation of Shanghai(No.09ZR1414800)Shanghai Applied Materials Collaborative Research Program(No:09520714400)
文摘One-dimensional Ni nanostructures were synthesized via a hydrazine reduction route under external magnetic fields. The mixture of de-ionized water and ethanol was used as the reaction solvent and hydrazine hydrate as reducing agents. The morphology and properties of Ni nanostructures were characterized by X-ray diffractometer(XRD), scanning electron microscopy(SEM), and vibrating sample magnetometer(VSM). It was found that the magnetic field strength, concentration of Ni ions,reaction time and temperature as well as p H values played key roles on formation, microstructures and magnetic properties of Ni nanowires. The optimal wires have diameter of ~200 nm and length up to ~200 μm. And their coercivity is ~260 Oe, which is much larger than the commercial Ni powders of 31 Oe. This work presents a simple, low-cost, environment-friendly and large-scale production approach to fabricate one-dimensional magnetic materials. The resulting materials may have potential applications in conductive filters, magnetic sensors and catalytic agents.
基金M/s NALCO, Bhubaneswar for the partial financial support to carry out this work
文摘Aluminium hydroxide precipitation from synthetic sodium aluminate solution was studied in the presence of hydrazine or hydrogen peroxide. The addition of low concentration of hydrazine is found to be effective, while higher amount of hydrogen peroxide is required to generate similar effect. XRD data confirm the product phase to be gibbsitic by nature. The scanning electron micrographs （SEM） show that agglomerated products form in the presence of hydrazine while fine discrete particles are produced with hydrogen peroxide. The probable mechanism of precipitation in the presence of hydrazine and hydrogen peroxide is also discussed.
