Heteroatoms doped iron oxide-based catalyst prepared from zinc slag for efficient selective catalytic reduction of NO_(x) with NH_(3)

Excessive emissions of nitrogen oxides from flue gas have imposed various detrimental impacts on environment,and the development of deNO_(x) catalysts with low-cost and high performance is an urgent requirement.Iron oxide-based material has been explored for promising deNO_(x) catalysts.However,the unsatisfactory low-temperature activity limits their practical applications.In this study,a series of excellent low-temperature denitrification catalysts(Ha-FeO_(x)/yZS)were prepared by acid treatment of zinc slag,and the mass ratios of Fe to impure ions was regulated by adjusting the acid concentrations.Ha-FeO_(x)/yZS showed high denitrification performance(>90%)in the range of 180–300℃,and the optimal NO conversion and N2 selectivity were higher than 95%at 250℃.Among them,the Ha-FeO_(x)/2ZS synthesized with 2 mol/L HNO3 exhibited the widest temperature window(175–350℃).The excellent denitrification performance of Ha-FeO_(x)/yZS was mainly attributed to the strong interaction between Fe and impurity ions to inhibit the growth of crystals,making Ha-FeO_(x)/yZS with amorphous structure,nice fine particles,large specific surface area,more surface acid sites and high chemisorbed oxygen.The in-situ DRIFT experiments confirmed that the SCR reaction on the Ha-FeO_(x)/yZS followed both Langmuir-Hinshelwood(L-H)mechanism and Eley-Rideal(E-R)mechanism.The present work proposed a high value-added method for the preparation of cost-effective catalysts from zinc slag,which showed a promising application prospect in NO_(x) removal by selective catalytic reduction with ammonia.

Propane dehydrogenation catalyzed by in-situ partially reduced zinc cations confined in zeolites

Propane dehydrogenation(PDH), employing Pt-or Cr-based catalysts, represents an emerging industrial route for propylene production. Due to the scarcity of platinum and the toxicity of chromium, alternative PDH catalysts are being pursued. Herein, we report the construction of Zn-containing zeolite catalysts,namely Zn@S-1, for PDH reaction. Well-isolated zinc cations are successfully trapped and stabilized by the Si-OH groups in S-1 zeolites via in-situ hydrothermal synthesis. The as-prepared Zn@S-1 catalysts exhibit good dehydrogenation activity, high propylene selectivity, and regeneration capability in PDH reaction under employed conditions. The in-situ partial reduction of zinc species is observed and the partially reduced zinc cations are definitely identified as the active sites for PDH reaction.

Effect of preparation methods on the structure and catalytic performance of Fe–Zn/K catalysts for CO2 hydrogenation to light olefins

Potassium promoted iron–zinc catalysts prepared by co-precipitation method(C–Fe–Zn/K),solvothermal method(S–Fe–Zn/K)and hydrothermal method(H–Fe–Zn/K)could selectively convert CO_2to light olefins,respectively.The physicochemical properties of the obtained catalysts were determined by SEM,N_2physisorption,XRD,H_2-TPR,CO_2-TPD and XPS measurements.The results demonstrated that preparation methods had great influences on the morphology,phase structures,reduction and adsorption behavior,and hence the catalytic performance of the catalysts.The samples prepared by hydrothermal and co-precipitation method generated small uniform particles and led to lower specific surface area.In contrast,microspheres with larger specific surface area were formed by self-assembly of nanosheets using solvothermal method.ZnFe_2O_4was the only detectable phase in the fresh C–2Fe–1Zn/K,S–3Fe–1Zn/K and S–2Fe–1Zn/K samples.ZnFe_2O_4and ZnO co-existed with increasing Zncontent in S–1Fe–1Zn/K sample,while ZnO and Fe_2O_3could be observed over H–2Fe–1Zn/K sample.All the used samples contained Fe_3O_4,ZnO and Fe_5C_2.The peak intensity of ZnO was strong in the AR-H–2Fe–1Zn/K sample while it was the lowest in the AR-C–2Fe–1Zn/K sample after reaction.The formation of ZnFe_2O_4increased the interaction between iron and zinc for C–2Fe–1Zn/K and S–Fe–Zn/K samples,causing easier reduction of Fe_2O_3to Fe_3O_4.The surface basicity of the sample prepared by co-precipitation method was much more than that of the other two methods.During CO_2hydrogenation,all the catalysts showed good activity and olefin selectivity.The CO selectivity was increased with increasing Zncontent over S–Fe–Zn/K samples.H–2Fe–1Zn/K catalyst preferred to the production of C_5^+hydrocarbons.CO_2conversion of 54.76%and C_2~=–C_4~=contents of 57.38%were obtained on C–2Fe–1Zn/K sample,respectively.

Identification of the highly active Zn-N_(4) sites with pyrrole/pyridine-N synergistic coordination by dz^(2)+s-band center for electrocatalytic H_(2)O_(2) production

Single metal atoms anchored on nitrogen-doped carbon materials(M-N_(4))have been identified as effective active sites for catalyzing the two-electron oxygen reduction reaction(2e-ORR).However,the relationship between the local atomic/electronic environments of the M-N_(4) sites(metal atoms coordinated with different types of N species)and their catalytic activity for 2e-ORR has rarely been elaborated clearly,which imposes significant ambiguity for the rational design of catalysts.Herein,guided by the comprehensive density-functional theory calculations and predictions,a series of Zn-N_(4) single-atom catalysts(SACs)are designed with pyrrole/pyridine-N(N_(Po)/N_(Pd))synergistic coordination and prepared by controlling the pyrolysis temperature(600,700,and 800℃),Among them,the dominated Zn-N_(4) configurations with rationally combined N_(Po)/N_(Pd)coordination show~*OOH adsorption strength close to the optimal value,much superior to those with mono N species.Thus,the as-prepared catalyst exhibits a high H_(2)O_(2) selectivity of over 90%both in neutral and alkaline environments,with a superb H_(2)O_(2) yield of up to 33.63 mol g^(-1)h^(-1)in an alkaline with flow cell.More importantly,a new descriptor,dz^(2)+s band center,has been proposed,which is especially feasible for predicting the activity for metal types with fully occupied s and d orbitals.This work thus presents clear guidance for the rational design of highly active SACs toward ORR and provides a complement to the d-band theory for more accurately predicting the catalytic activity of the materials.

Zinc bis-Schiff base complexes： Synthesis, structure, and application in ring-opening polymerization of rac-lactide

A series of bis-ligated zinc complexes supported by Schitt base ligands were successfully synthesized and characterized by 1 H, 13C NMR, elemental analysis, and X-ray crystallography. These zinc complexes can be used as catalysts for the polymerization of rac-lactide in solution as well as in molten lactide. The results show that all catalysts exhibited high catalytic activity and obtained moderate heterotactic PLAs with the expected molecular weight. Complex 1 can catalyze the polymerization of rac-lactide under controllable conditions with living and immortal character in toluene solution. In addition, the steric hindrance and electronic effects has a great influence on the catalytic activity and selectivity of catalysts.

Lignin-derived Zn single atom/N-codoped porous carbon forα-alkylation of aromatic ketones with alcohols via borrowing hydrogen strategy

A green and scalable strategy has been developed for the synthesis of lignin-derived Zn single atom/N-codoped porous carbon(LCN@Zn-SAC)containing similar ZnNx sites with carbonic anhydrases.This catalyst exhibits superior activity on theα-alkylation of ketones with alcohols via borrowing hydrogen strategy(TON up to 15 h^(−1))than most of previously reported works.The dehydrogenation of benzyl alcohol is the rate-determining step based on kinetic experiment results.According to experimental and theoretical calculation results,Zn electron density is inversely proportional to reaction energy barriers,because Zn sites with less positive charge(ZnN_(4) and ZnN_(3)C)in Zn-SACs display better borrowing hydrogen ability than other Zn sites.Furthermore,this catalyst can be recycled by simple centrifugation,which can be reused at least 8 runs with no obvious lose in activity.To the best of our knowledge,this is the first example of non-noble metal-SAC-catalyzedα-alkylation via borrowing hydrogen strategy.

Preparation of Poly（serine ester）s by Ring-opening Polymerization of N-Trityl Serine Lactone Under Catalysis of ZnEt2

Poly（N-trityl serine lactone）（PTSL） and mPEG-block-poly（N-trityl serine lactone）（mPEG-b-PTSL, PEG= polyethylene glycol） were synthesized via the ring-opening polymerization of N-trityl serine lactone（TSL） with diethyl zinc（ZnEt2） as catalyst. The structures of these polymers were confirmed with hydrogen nuclear magnetic resonance（IH NMR） spectroscopy, carbon nuclear magnetic resonance（13C NMR） spectroscopy and infrared（IR） spectrometer. The thermal decomposition temperature and glass transition temperature of PTSL were 241 and 161 ℃, respectively. A series of mPEG-b-PTSL with different molecular weights（Mn＇s from 7000 to 32000） was obtained by tuning the TSL/mPEG feed ratio. After the removal of the trityl groups, mPEG-block-poly（serine lactone）（mPEG- b-PSL） was obtained as a new kind of cationic block copolymer. Low cytotoxicity of these polymers to L929 cells was confirmed via 3-（4,5-dimethylthiazol-2-yl）-2,5-diphenyltetrazolium bromide（MTT） assay.