Highly selective photocatalytic reduction of CO_(2) to CH_(4) on electron-rich Fe species cocatalyst under visible light irradiation

Efficient photocatalytic reduction of CO_(2) to high-calorific-value CH4,an ideal target product,is a blueprint for C_(1)industry relevance and carbon neutrality,but it also faces great challenges.Herein,we demonstrate unprecedented hybrid SiC photocatalysts modified by Fe-based cocatalyst,which are prepared via a facile impregnation-reduction method,featuring an optimized local electronic structure.It exhibits a superior photocatalytic carbon-based products yield of 30.0μmol g^(−1) h^(−1) and achieves a record CH_(4) selectivity of up to 94.3%,which highlights the effectiveness of electron-rich Fe cocatalyst for boosting photocatalytic performance and selectivity.Specifically,the synergistic effects of directional migration of photogenerated electrons and strongπ-back bonding on low-valence Fe effectively strengthen the adsorption and activation of reactants and intermediates in the CO_(2)→CH_(4) pathway.This study inspires an effective strategy for enhancing the multielectron reduction capacity of semiconductor photocatalysts with low-cost Fe instead of noble metals as cocatalysts.

Mild polarization electric field in ultra-thin BN-Fe-graphene sandwich structure for efficient nitrogen reduction

The electrocatalytic N_(2)reduction reaction(NRR)is expected to supersede the traditional Haber-Bosch technology for NH3 production under ambient conditions.The activity and selectivity of electrochemical NRR are restricted to a strong polarized electric field induced by the catalyst,correct electron transfer direction,and electron tunneling distance between bare electrode and active sites.By coupling the chemical vapor deposition method with the poly(methyl methacylate)-transfer method,an ultrathin sandwich catalyst,i.e.,Fe atoms(polarized electric field layer)sandwiched between ultrathin(within electron tunneling distance)BN(catalyst layer)and graphene film(conducting layer),is fabricated for electrocatalytic NRR.The sandwich catalyst not only controls the transfer of electrons to the BN surface in the correct direction under applied voltage but also suppresses hydrogen evolution reaction by constructing a neutral polarization electric field without metal exposure.The sandwich electrocatalyst NRR system achieve NH3 yield of 8.9μg h^(−1)cm^(−2)and Faradaic Efficiency of 21.7%.The N_(2)adsorption,activation,and polarization electric field changes of three sandwich catalysts(BN-Fe-G,BN-Fe-BN,and G-Fe-G)during the electrocatalytic NRR are investigated by experiments and density functional theory simulations.Driven by applied voltage,the neutral polarized electric field induced by BN-Fe-G leads to the high activity of electrocatalytic NRR.

Atomically dispersed Fe sites on hierarchically porous carbon nanoplates for oxygen reduction reaction

Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air batteries.Although Fe-N-C single atom catalysts(SACs) have been hailed as the most promising candidate due to the optimal binding strength of ORR intermediates on the Fe-N_(4) sites,they suffer from serious mass transport limitations as microporous templates/substrates,i.e.,zeolitic imidazolate frameworks(ZIFs),are usually employed to host the active sites.Motivated by this challenge,we herein develop a hydrogen-bonded organic framework(HOF)-assisted pyrolysis strategy to construct hierarchical micro/mesoporous carbon nanoplates for the deposition of atomically dispersed Fe-N_(4) sites.Such a design is accomplished by employing HOF nanoplates assembled from 2-aminoterephthalic acid(NH_(2)-BDC) and p-phenylenediamine(PDA) as both soft templates and C,N precursors.Benefitting from the structural merits inherited from HOF templates,the optimized catalyst(denoted as Fe-N-C SAC-950) displays outstanding ORR activity with a high half-wave potential of 0.895 V(vs.reversible hydrogen electrode(RHE)) and a small overpotential of 356 mV at 10 mA cm^(-2) for the oxygen evolution reaction(OER).More excitingly,its application potential is further verified by delivering superb rechargeability and cycling stability with a nearly unfading charge-discharge gap of 0.72 V after 160 h.Molecular dynamics(MD) simulations reveal that micro/mesoporous structure is conducive to the rapid mass transfer of O_(2),thus enhancing the ORR performance.In situ Raman results further indicate that the conversion of O_(2) to~*O_(2)-the rate-determining step(RDS) for Fe-N-C SAC-950.This work will provide a versatile strategy to construct single atom catalysts with desirable catalytic properties.

Dissimilatory reduction of Fe^III (EDTA) with microorganisms in the system of nitric oxide removal from the flue gas by metal chelate absorption

In the system of nitric oxide removal from the flue gas by metal chelate absorption, it is an obstacle that ferrous absorbents are easily oxidized by oxygen in the flue gas to ferric counterparts, which are not capable of binding NO. By adding iron metal or electrochemical method, Fe III (EDTA) can be reduced to Fe II (EDTA). However, there are various drawbacks associated with these techniques. The dissimilatory reduction of Fe III (EDTA) with microorganisms in the system of nitric oxide removal by metal chelate absorption was investigated. Ammonium salt instead of nitrate was used as the nitrogen source, as nitrates inhibited the reduction of Fe III due to the competition between the two electron acceptors. Supplemental glucose and lactate stimulated the formation of Fe II more than ethanol as the carbon sources. The microorganisms cultured at 50℃ were not very sensitive to the other experimental temperature, the reduction percentage of Fe III varied little with the temperature range of 30—50℃. Concentrated Na 2CO 3 solution was added to adjust the solution pH to an optimal pH range of 6—7 The overall results revealed that the dissimilatory ferric reducing microorganisms present in the mix culture are probably neutrophilic, moderately thermophilic Fe III reducers.

Experimental study on the inhibition of biological reduction of Fe(III)EDTA in NO_x absorption solution

Scrubbing of NOx from the gas phase with Fe(II)EDTA has been shown to be highly effective. A new biological method can be used to convert NO to N2 and regenerate the chelating agent Fe(II)EDTA for continuous NO absorption. The core of this biological regeneration is how to effectively simultaneous reduce Fe(III)EDTA and Fe(II)EDTA-NO, two mainly products in the ferrous chelate absorption solution. The biological reduction rate of Fe(III)EDTA plays a main role for the NOx removal efficiency. In this paper, a bacterial strain identified as Klebsiella Trevisan sp. was used to demonstrate an inhibition of Fe(III)EDTA reduction in the presence of Fe(II)EDTA-NO. The competitive inhibition experiments indicted that Fe(II)EDTA-NO inhibited not only the growth rate of the iron-reduction bacterial strain but also the Fe(III)EDTA reduction rate. Cell growth rate and Fe(III)EDTA reduction rate decreased with increasing Fe(II)EDTA-NO concentration in the solution.

Non-isothermal reduction kinetics of Fe_2O_3-NiO composites for formation of Fe-Ni alloy using carbon monoxide

The non-isothermal reduction kinetics and mechanism of Fe2O3-NiO composites with different Fe2O3-NiO compacts using carbon monoxide as reductant were investigated. The results show that the reduction degree increases rapidly with increasing the content of NiO, and the presence of NiO also improves the reduction rate of iron oxides. It is found that NiO is preferentially reduced at the beginning of the reactions, and then the metallic Ni acts as a catalyst promoting the reduction rate of iron oxides. It is also observed that the increase of the Ni O content enhances the formation of awaruite(FeNi3) but decreases the percentage of kamacite(Fe,Ni) and taenite(Fe,Ni). The particle size of the materials tends to be uniform during the reduction process due to the presence of metallic nickel, metallic iron and the formation of Fe-Ni alloy. The concentration of CO in the product gas is greater than that of CO2 at the beginning of the reaction and then slows down. The fastest reduction rate of Fe2O3-NiO composites with CO appears at 400-500 °C, and nucleation growth model can be used to elucidate the reduction mechanism. Nucleation growth process is found to be the rate controlling step when the temperature is lower than 1000 °C.

Fe-Beta zeolite for selective catalytic reduction of NO_x with NH_3:Influence of Fe content

Fe doped Beta zeolite with different Fe contents were prepared by ion exchange by changing the volume or the concentration of a Fe salt solution. For a particular mass of Fe salt precursor, the concentration of the metal salt solution during ion exchange influenced the ion exchange capacity of Fe, and resulted in different activities of the Fe-Beta catalyst. Fe-Beta catalysts with the Fe contents of （2.6, 6.3 and 9） wt% were synthesized using different amounts of 0.02 mol/L Fe salt solution. These catalysts were studied by various characterization techniques and their NH3-SCR activities were evaluated. The Fe-Beta catalyst with the Fe content of 6.3 wt% exhibited the highest activity, with a temperature range of 202-616℃ where the NOx conversion was 〉 80%. The Fe content in Beta zeolite did not influence the structure of Beta zeolite and valence state of Fe. Compared with the Fe-Beta catalysts with low Fe content （2.6 wt%）, Fe-Beta catalysts with 6.3 wt% Fe content possessed more isolated Fe3. active sites which led to its higher NH3-SCR activity. A high capacity for NH3 and NO adsorption, and a high activity for NO oxidation also contributed to the high NH3-SCR activity of the Fe-Beta catalyst with 6.3 wt%. However, when the Fe content was further increased to 9.0 wt%, the amount of FexOy nanoparticles increased while the amount of isolated Fe3＋ active sites was unchanged, which promoted NH3 oxidation and decreased the NH3-SCR activity at high temperature.

Dissimilatory Fe(Ⅲ) reduction characteristics of paddy soil extract cultures treated with glucose or fatty acids

Dissimilatory Fe(Ⅲ) reduction is a universal process with irreplaceable biological and environmental importance in anoxic environments. Our knowledge about Fe(Ⅲ) reduction predominantly comes from pure cultures of dissimilatory Fe(Ⅲ) reducing bacteria (DFRB). The objective of this study was to compare the effects of glucose and a selection of short organic acids (citrate, succinate, pyruvate, propionate, acetate, and formate) on Fe(Ⅲ) reduction via the anaerobic culture of three paddy soil solutions with Fe...

Comparison of reduction behavior of Fe_2O_3, ZnO and ZnFe_2O_4 by TPR technique

Advanced integrated gasification combined cycle （IGCC） power generation systems require the development of high-temperature, regenerable, desulfurization sorbents capable of removing hydrogen sulfide from coal gasifier gas to very low levels. As a sort of effective desufurizer, such as Fe2O3, ZnO and ZnFe2O4, it will endure strong reducing atmosphere in desulfurization process. The reduced degree of desufurizer can have an effect on its desulfurization reactivity. In this paper, Fe2O3, ZnO and ZnFe2O4 were synthesized by precipitation or co-precipitation at constant pH. After aging, washing and drying, the solids were calcined at 800℃. The reduction behaviors of sample were characterized by temperature-programmed reduction （TPR）. It is found that there are two reduction peaks for Fe2O3 in TPR, and whereas no reduction peaks for ZnO are found. The reduction process of ZnFe2O4 prepared by co-precipitation is different from that of Fe2O3. ZnFe2O4 is easier to be reduced than Fe2O3. The activation energy of reduction process for Fe2O3 and ZnFe2O4 is obtained at different reduction periods.

Effect of Fe(Ⅲ) on the bromate reduction by humic substances in aqueous solution

Humic substances are ubiquitous redox-active organic compounds of environment. In this study, experiments were conducted to determine the reduction capacity of humic acid in the man-ix of bromate and Fe（Ⅲ） solutions and the role of Fe（Ⅲ） in this redox process. The results showed that the humic acid regenerated Fe（Ⅱ） and reduced bromate abiotically. The addition of Fe（Ⅲ） could accelerate the bromate reduction rate by forming humic acid-Fe（Ⅲ） complexes. Iron species acts as electron mediator and catalyst for the bromate reduction by humic acid, in which humic acid transfers electrons to the complexed Fe（Ⅲ） to form Fe（Ⅱ）, and the regenerated Fe（Ⅱ） donate the electrons to bromate. The kinetics study on bromate reduction further indicated that bromate reduction by humic acid-Fe（Ⅲ） complexes is pH dependent. The rate decreased by 2-fold with the increase in solution pH by one unit. The reduction capacity of Aldrich humic acid was observed to be lower than that of humic acid or natural organic matter of Suwanne River, indicating that such redox process is expected to occur in the environment.

Reaction behavior of kaolinite with ferric oxide during reduction roasting

The pre-separation of silica and alumina in aluminosilicates is of great significance for efficiently treating alumina-/ silica-bearing minerals for alumina production. In this work, the reaction behavior of kaolinite with ferric oxide during reduction roasting was investigated. The results of thermodynamic analyses and reduction roasting experiments show that ferrous oxide obtained from ferric oxide reduction preferentially reacts with alumina in kaolinite to form hercynite, meanwhile the silica in kaolinite is transformed into quartz solid solution and/or cristobalite solid solution. With increasing roasting temperature, fayalite formed by reaction of surplus ferrous oxide with silica at low temperature is reduced to silica and metallic iron in the presence of sufficient carbon dosage. However, increasing roasting temperature and decreasing Fe2O3/Al2O3 molar ratio favor mullite formation. The complete conversion of kaolinte into free silica and hercynite can be obtained by roasting raw meal of kaolin, ferric oxide and coal powder with Fe2O3/Al2O3/C molar ratio of 1.2:2.0:1.2 at 1373 K for 60 min. This work may facilitate the development of a technique for comprehensively utilizing silica and alumina in aluminosilicates.

Low-Temperature Selective Catalytic Reduction of NO with NH_3 over Fe–Ce–O_x Catalysts

In this study, we used a simple impregnation method to prepare Fe-Ce-O x catalysts and tested them regarding their low-temperature (200-300 °C) selective catalytic reduction (SCR) of NO using NH3. We investigated the effects of Fe/Ce molar ratio, the gas hourly space velocity (GHSV), the stability and SO2/H2O resistance of the catalysts. The results showed that the FeCe(1:6)O x (Ce/Fe molar ratio is 1:6) catalyst, which has some ordered parallel channels, exhibited good SCR performance. The FeCe(1:6)O x catalyst had the highest NO conversion with an activity of 94-99% at temperatures between 200 and 300 °C at a space velocity of 28,800 h−1. The NO conversion for the FeCe(1:6)O x catalyst also reached 80-98% between 200 and 300 °C at a space velocity of 204,000 h−1. In addition, the FeCe(1:6)O x catalyst demonstrated good stability in a 10-h SCR reaction at 200-300 °C. Even in the presence of SO2 and H2O, the FeCe(1:6)O x catalyst exhibited good SCR performance.

Boron modulating electronic structure of FeN4C to initiate high-efficiency oxygen reduction reaction and high-performance zinc-air battery

The biggest challenge is to develop a low cost and readily available catalyst to replace expensive commercial Pt/C for efficient electrochemical oxygen reduction reaction(ORR).In this research,closo-[B_(12)H_(12)]^(2−)and 1,10-phenanthroline-iron complexes were introduced into the porous metal-organic framework by impregnation method,and further annealing treatment achieved the successful anchoring of single-atom-Fe in B-doped CN Matrix(FeN4CB).The ORR activity of FeN4CB is comparable to the widely used commercial 20 wt%Pt/C.Where the half-wave potential(E_(1/2))in alkaline medium up to 0.84 V,and even in the face of challenging ORR in acidic medium,the E_(1/2)of ORR driven by FeN4CB is still as high as 0.81 V.When FeN4CB was used as air cathode,the open circuit voltage of Zn-air battery reaches 1.435 V,and the power density and specific capacity are as high as 177 mW cm^(−2)and 800 mAh g_(Zn)^(−1)(theoretical value:820 mAh g_(Zn)^(−1)),respectively.The dazzling point of FeN4CB also appears in the high ORR stability,whether in alkaline or acidic media,E_(1/2)and limiting current density are still close to the initial value after 5000 times cycles.After continuously running the charge-discharge test for 220 h,the charge voltage and discharge voltage of the rechargeable zinc-air battery with FeN4CB as the air cathode maintained the initial state.Density functional theory calculations reveals that introducing B atom to Fe–N4–C can adjust the electronic structure to easily break O=O bond and significantly reduce the energy barrier of the rate-determining step resulting in an improved ORR activity.

Enhanced photocatalytic Cr(Ⅵ) reduction and diclofenac sodium degradation under simulated sunlight irradiation over MIL-100(Fe)/g-C_3N_4 heterojunctions

Metal‐organic framework MIL‐100(Fe)and g‐C3N4 heterojunctions(MG‐x,x=5%,10%,20%,and 30%,x is the mass fraction of MIL‐100(Fe)in the hybrids)were facilely fabricated through ball‐milling and annealing,and characterized by powder X‐ray diffraction,Fourier transform infrared spectroscopy,thermogravimetric analysis,transmission electron microscopy,UV‐visible diffuse‐reflectance spectrometry,and photoluminescence emission spectrometry.The photocatalytic activities of the series of MG‐x heterojunctions toward Cr(VI)reduction and diclofenac sodium degradation were tested upon irradiation with simulated sunlight.The influence of different organic compounds(ethanol,citric acid,oxalic acid,and diclofenac sodium)as hole scavengers and the pH values(2,3,4,6,and 8)on the photocatalytic activities of the series of MG‐x heterojunctions was investigated.MG‐20%showed superior photocatalytic Cr(VI)reduction and diclofenac sodium degradation performance than did the individual MIL‐100(Fe)and g‐C3N4 because of the improved separation of photoinduced electron‐hole charges,which was clarified via photoluminescence emission and electrochemical data.Moreover,the MG‐x exhibited good reusability and stability after several runs.

Effect of Mn addition and refining process on Fe reduction of Mg−Mn alloys made from magnesium scrap

The Fe reduction,microstructure evolution and corrosion susceptibility of Mg−Mn alloys made from magnesium scrap refining with Mn addition were investigated.The results show that significant Fe content change occurs during near-solid-melt treatment(NSMT)process even in the absence of Mn,because of the high saturation of Fe in the melt.Furthermore,in the NSMT process,even a small amount of Mn addition can lead to a sharp deposition of Mn atoms.The NSMT process can increase the growth rate of the Fe-rich particles,and then accelerate their sinking movement.Nevertheless,the addition of Mn hinders the coarsening process of Fe-rich particles.Besides,the corrosion susceptibility of the alloys is mainly affected by the solubility of Fe,which can be significantly reduced by Mn addition.Moreover,the presence of more Fe-rich particles does not necessarily increase the corrosion susceptibility of the alloy.Consequently,in the refining process of Mg−Mn alloys made from magnesium scrap,on the basis of NSMT process and adding an appropriate Mn content(about 0.5 wt.%),the purity of the melt can be improved,thereby obtaining an alloy with excellent corrosion resistance.

Solid phase microwave-assisted fabrication of Fe-doped ZIF-8 for single-atom Fe-N-C electrocatalysts on oxygen reduction

Fe-N-C endowed with inexpensiveness,high activity,and excellent anti-poisoning power have emerged as promising candidate catalysts for oxygen reduction reaction(ORR).Single-atom Fe-N-C electrocatalysts derived from Fe-doped ZIF-8 represent the top-level ORR performance.However,the current fabrication of Fe-doped ZIF-8 relies on heavy consumption of time,energy,cost and organic solvents.Herein,we develop a rapid and solvent-free method to produce Fe-doped ZIF-8 under microwave irradiation,which can be easily amplified in combination with ball-milling.After rational pyrolysis,Fe-N-C catalysts with atomic FeN4 sites well dispersed on the hierarchically porous carbon matrix are obtained,which exhibit exceptional ORR performance with a half-wave potential of 0.782 V(vs.reversible hydrogen electrode(RHE))and brilliant methanol tolerance.The assembled direct methanol fuel cells(DMFCs)endow a peak power density of 61 mW cm^(-2) and extraordinary stability,highlighting the application perspective of this strategy.

REDUCTION OF FERRIC IRON IN THE TITANIUM SULFATE SOLUTION BY THE ION EXCHANGE MEMBRANE PRIMARY CELL METHOD

In the production process of titanium dioxide with sulfuric acid, the contamination of the titanium sulfate solution (the ilmenite leaching solution) in the Fe 3+ reduction stage by iron scraps is a practical problem because it is difficult to guarantee the quality of the iron scraps. In this research, a new method, called the ion exchange membrane primary cell method, for reduction of Fe 3+ in the titanium sulfate solution has been advanced. The positive compartment of the primary cell consists of lead (copper) electrode and the titanium sulfate solution, and the negative compartment consists of iron electrode and acidic FeSO 4 solution. The anion ion exchange membrane is used as the diaphragm between two compartments. Fe 3+ in the titanium sulfate solution is reduced by the electric discharge of the primary cell. The effects of temperature, stirring strength of the solution and membrane area on the reduction rate have been investigated. The experimental result shows that the optimum current density can be higher than 100 A/m 2.

High efficient oxygen reduction performance of Fe/Fe3C nanoparticles in situ encapsulated in nitrogen-doped carbon via a novel microwave-assisted carbon bath method

Fe-based carbon materials are widely considered promising to replace Pt/C as next-generation electrocatalysts towards oxygen reduction reaction (ORR). However, the preparation of Fe-based carbon materials is still carried out by conventional heating method (CHM). Herein, a novel microwave-assisted carbon bath method (MW-CBM) was proposed, which only took 35 min to synthesize Fe/Fe3C nanoparticles encapsulated in N-doped carbon layers derived from Prussian blue (PB). The catalyst contained large specific surface area and mesoporous structure, abundant Fe-Nx and C–N active sites, unique core-shell structure. Due to the synergistic effects of these features, the as-prepared Fe/Fe3C@NC-2 displayed outstanding ORR activity with onset potential of 0.98 VRHE and halfwave potential of 0.87 VRHE, which were more positive than 20 wt.% Pt/C (0.93 VRHE and 0.82 VRHE). Besides, Fe/Fe3C@NC-2 gave a better stability and methanol tolerance than Pt/C towards ORR in alkaline media, too.

Inducing Fe 3d Electron Delocalization and Spin‑State Transition of FeN_(4) Species Boosts Oxygen Reduction Reaction for Wearable Zinc–Air Battery

Transition metal-nitrogen-carbon materials(M-N-Cs),particularly Fe-N-Cs,have been found to be electroactive for accelerating oxygen reduction reaction(ORR)kinetics.Although substantial efforts have been devoted to design Fe-N-Cs with increased active species content,surface area,and electronic conductivity,their performance is still far from satisfactory.Hitherto,there is limited research about regulation on the electronic spin states of Fe centers for Fe-N-Cs electrocatalysts to improve their catalytic performance.Here,we introduce Ti_(3)C_(2) MXene with sulfur terminals to regulate the electronic configuration of FeN_(4) species and dramatically enhance catalytic activity toward ORR.The MXene with sulfur terminals induce the spin-state transition of FeN_(4) species and Fe 3d electron delocalization with d band center upshift,enabling the Fe(II)ions to bind oxygen in the end-on adsorption mode favorable to initiate the reduction of oxygen and boosting oxygen-containing groups adsorption on FeN_(4) species and ORR kinetics.The resulting FeN_(4)-Ti_(3)C_(2)Sx exhibits comparable catalytic performance to those of commercial Pt-C.The developed wearable ZABs using FeN_(4)-Ti_(3)C_(2)Sx also exhibit fast kinetics and excellent stability.This study confirms that regulation of the electronic structure of active species via coupling with their support can be a major contributor to enhance their catalytic activity.

Boost oxygen reduction reaction performance by tuning the active sites in Fe-N-P-C catalysts

Cost-effective atomically dispersed Fe-N-P-C complex catalysts are promising to catalyze the oxygen reduction reaction(ORR)and replace Pt catalysts in fuel cells and metal-air batteries.However,it remains a challenge to increase the number of atomically dispersed active sites on these catalysts.Here we report a highly efficient impregnation-pyrolysis method to prepare effective ORR electrocatalysts with large amount of atomically dispersed Fe active sites from biomass.Two types of active catalyst centers were identified,namely atomically dispersed Fe sites and Fe_(x)P particles.The ORR rate of the atomically dispersed Fe sites is three orders of magnitude higher than it of Fe_(x)P particles.A linear correlation between the amount of the atomically dispersed Fe and the ORR activity was obtained,revealing the major contribution of the atomically dispersed Fe to the ORR activity.The number of atomically dispersed Fe increases as the Fe loading increased and reaching the maximum at 1.86 wt%Fe,resulting in the maximum ORR rate.Optimized Fe-N-P-C complex catalyst was used as the cathode catalyst in a homemade Zn-air battery and good performance of an energy density of 771 Wh kgZn^(-1),a power density of 92.9 m W cm^(-2) at 137 m A cm^(-2) and an excellent durability were exhibited.