Improved Catalytic Reaction of Biotemplated Palladium Nanoparticles through Immobilized Metal Affinity Purification

To investigate the effect purification plays on nanoparticle (NP) synthesis and catalytic activity, three copies of Pd4 (TSNAVHPTLRHL) fused to the N-terminus of Green Fluorescent Protein (GFP) was produced recombinantly and its characteristics pre and post purification was assessed. An E. coli expression system was employed, and purification was performed with Immobilized Metal Affinity Column (IMAC). Transmission electron microscopy (TEM) was utilized to examine the morphology of NPs synthesized with an enriched protein sample and ImageJ was used to determine the average size to be 2.44 nm. The turnover frequency of fabricated NP from the purified protein was analyzed by a model Suzuki-Miyaura coupling reactions and determined to be 33,000 hr-1. This value is three times higher than the turnover frequency when crude lysate containing (Pd4)3-GFP was used during NP synthesis. This result shows that enrichment enhanced the catalytic activity of NP.

In situ evolution of surface Co_(2)CrO_(4) to CoOOH/CrOOH by electrochemical method:Toward boosting electrocatalytic water oxidation

Developing non‐noble‐metal electrocatalyst with efficient and durable activity is a urgent task for addressing the sluggish reaction kinetics of electrochemical water oxidation.Structural evolution of the electrocatalyst is an important strategy for achieving enhanced performance.Herein,in situ evolution of surface Co_(2)CrO_(4) to CoOOH/CrOOH(CoOOH/CrOOH‐Co_(2)CrO_(4))by an electrochemical method under alkaline conditions was designed for enhancing the electrocatalytic performance of water oxidation.The experiments demonstrated that the synergy between CoOOH/CrOOH and Co_(2)CrO_(4) resulted in a marked increase in the number of active sites and improved the rate of charge transfer,which enhanced the activity for water oxidation.At a geometrical current density of 20 mA cm^(−2),the overpotential of the oxygen evolution reaction was 244 mV and the turnover frequency was 0.536 s^(−1) in 1.0 M NaOH.

Effect of noble metal nanoparticle size on C–N bond cleavage performance in hydrodenitrogenation: a study of active sites

Breakage of the C-N bond is a structure sensitive process,and the catalyst size significantly affects its activity.On the active metal nanoparticle scale,the role of catalyst size in C-N bond cleavage has not been clearly elucidated.So,Ru catalysts with variable nanoparticle sizes were obtained by modulating the reduction temperature,and the catalytic activity was evaluated using 1,2,3,4-tetrahydroquinoline and o-propylaniline with different C-N bond hybridization patterns as reactants.Results showed a 13 times higher reaction rate for sp3-hybridized C-N bond cleavage than sp2-hybridized C-N bond cleavage,while the reaction rate tended to increase first and then decrease as the catalyst nanoparticle size increased.Different concentrations of terrace,step,and corner sites were found in different sizes of Ru nanoparticles.The relationship between catalytic site variation and C-N bond cleavage activity was further investigated by calculating the turnover frequency values for each site.This analysis indicates that the variation of different sites on the catalyst is the intrinsic factor of the size dependence of C-N bond cleavage activity,and the step atoms are the active sites for the C-N bond cleavage.When Ru nanoparticles are smaller than 1.9 nm,they have a strong adsorption effect on the reactants,which will affect the catalytic performance of the Ru catalyst.Furthermore,these findings were also confirmed on other metallic Pd/Pt catalysts.The role of step sites in C-N bond cleavage was proposed using the density function theory calculations.The reactants have stronger adsorption energies on the step atoms,and step atoms have d-band center nearer to the Fermi level.In this case,the interaction with the reactant is stronger,which is beneficial for activating the C-N bond of the reactant.

Surface Active Sites on Co_(3)O_(4) Nanobelt and Nanocube Model Catalysts for CO Oxidation

CO oxidation has been performed on Co_(3)O_(4) nanobelts and nanocubes as model catalysts.The Co_(3)O_(4) nanobelts which have a predominance of exposed{011}planes are more active than Co_(3)O_(4) nanocubes with exposed{001}planes.Temperature programmed reduction of CO shows that Co_(3)O_(4) nanobelts have stronger reducing properties than Co_(3)O_(4) nanocubes.The essence of shape and crystal plane effect is revealed by the fact that turnover frequency of Co3+sites of{011}planes on Co_(3)O_(4) nanobelts is far higher than that of{001}planes on Co_(3)O_(4) nanocubes.

Highly efficient overall urea electrolysis via single-atomically active centers on layered double hydroxide

Anodic urea oxidation reaction(UOR)is an intriguing half reaction that can replace oxygen evolution reaction(OER)and work together with hydrogen evolution reaction(HER)toward simultaneous hydrogen fuel generation and urea-rich wastewater purification;however,it remains a challenge to achieve overall urea electrolysis with high efficiency.Herein,we report a multifunctional electrocatalyst termed as Rh/Ni V-LDH,through integration of nickel-vanadium layered double hydroxide(LDH)with rhodium single-atom catalyst(SAC),to achieve this goal.The electrocatalyst delivers high HER mass activity of0.262 A mg^(-1) and exceptionally high turnover frequency(TOF)of 2.125 s^(-1) at an overpotential of100 m V.Moreover,exceptional activity toward urea oxidation is addressed,which requires a potential of 1.33 V to yield 10 mA cm^(-2),endorsing the potential to surmount the sluggish OER.The splendid catalytic activity is enabled by the synergy of the Ni V-LDH support and the atomically dispersed Rh sites(located on the Ni-V hollow sites)as evidenced both experimentally and theoretically.The selfsupported Rh/Ni V-LDH catalyst serving as the anode and cathode for overall urea electrolysis(1 mol L^(-1) KOH with 0.33 mol L^(-1) urea as electrolyte)only requires a small voltage of 1.47 V to deliver 100 mA cm^(-2) with excellent stability.This work provides important insights into multifunctional SAC design from the perspective of support sites toward overall electrolysis applications.

Carbon monoxide powered fuel cell towards H_(2)-onboard purification

Proton exchange membrane fuel cells(PEMFCs)suffer extreme CO poisoning even at PPM level(<10 ppm),owning to the preferential CO adsorption and the consequential blockage of the catalyst surface.Herein,however,we report that CO itself can become an easily convertible fuel in PEMFC using atomically dispersed Rh catalysts(Rh-N-C).With CO to CO_(2) conversion initiates at 0 V,pure CO powered fuel cell attains unprecedented power density at 236 mW cm^(-2),with maximum CO turnover frequency(64.65 s^(-1),363 K)far exceeding any chemical or electrochemical catalysts reported.Moreover,this feature enables efficient CO selective removal from H_(2) gas stream through the PEMFC technique,with CO concentration reduced by one order of magnitude through running only one single cell,while simultaneously harvesting electricity.We attribute such catalytic behavior to the weak CO adsorption and the co-activation of H_(2)O due to the interplay between two adjacent Rh sites.

Steam effects over Pd/Ce_(0.67)Zr_(0.33)O_2 three-way catalyst

In the purification process of automobile exhaust,existing water plays an important role as an oxidant,which converts CO and hydrocarbons（HCs） by the water-gas shift（WGS） and the steam reforming（SR） reactions,respectively,especially at high temperatures.Meanwhile it is major component of the exhaust which can affect significantly the thermal stability of the three-way catalyst.Activity experiments were carried out close to the real operation conditions（GHSV,concentration,etc.） with a Pd/Ce0.67Zr0.33O2 catalyst supplying information on the CO and C3H8 oxidation reactions in feedstream formed by different reactant combinations.The obtained results showed that the activity of the CO and C3H8 oxidation was promoted by the addition of steam due to the WGS and SR reactions.The WGS and SR reaction were competitive under oxygen-lean conditions.The kinetic analysis was considered for WGS and SR reactions.

CO and C3Hs Total Oxidation over Pd Catalysts Supported on Commercial Ce-Zr Solid Solution： Effects of the Calcination Temperature and Hydrothermal Treatment

A series of Pd catalysts supported on commercial Ce-Zr solid solution（Pd/CZ） calcined at different tem- peratures（750, 900 and 1050 %℃） was prepared via an incipient wetness impregnation method. The activities of the fresh and hydrothermally aged PdTCZ catalysts were tested for total oxidation of CO and C3H8. For CO oxidation, the activity of either fresh or aged Pd/CZ catalysts decreased with the elevating of calcination temperature of CZ support, with a fresh catalyst calcined at 750 ℃ possessing the highest activity and hydrothermal stability. For C3H8 total oxidation, the activity of Pd/CZ catalysts could be improved by increasing the calcination temperature of support. However, the aged Pd/CZ catalysts showed higher activity than corresponding fresh Pd/CZ catalysts. The turnover frequency（TOF） over Pd/CZ catalyst for CO oxidation increased with increasing reduction ability of the catalysts, with a fresh catalyst calcined at 750 ℃ having the highest value（0.27 s^-1）. However, the TOF of Pd/CZ catalyst for C3Hs total oxidation was mainly affected by the size of Pd particles, and large Pd particles possessed a higher activity, with the highest TOF value（0.96s^-1） obtained over an aged catalyst calcined at 1050 ℃.

N2O Decomposition Catalyzed by K＋-doped Bi0.02Co

K＋-doped Bi0.02Co was investigated as catalyst for N2O decomposition. It was found that the catalytic performance of the Bi0.02Co catalyst, which was prepared by coprecipitation method, can be effectively modified by potassium cations via impregnation. The optimized K0.01Bi0.02Co catalyst exhibited much higher activity compared with Bi0.02Co and K0.01Co for the reaction in feed gas 0.2% N2O/Ar, irrespective of the presence or absence of impurity gas（volume fraction） 5%02, 2%H20, 0.12%NO and 10%CO2. Characterization of the catalysts with H2 temperature programmed reduction（H2-TPR） and O2 temperature programmed desorption（O2-TPD） indicate that the Co--O bond in Bi0.02Co was weakened by the K＋ doping, and hence the K0.01Bi0.02Co catalyst has much higher turnover frequency（TOF） than CO3O4 spinel and Bi0.02Co for the reaction.

CO and C_3H_8 total oxidation over Pd/La-Al_2O_3 catalysts: Effect of calcination temperature and hydrothermal treatment

A series of Pd/La-Al2O3（PLA） catalysts with La-Al2O3（LA） support calcined at different temperatures（500, 700, 900 and 1050 oC） were prepared using an incipient wetness impregnation method. The activity of the fresh and hydrothermally aged PLA catalysts were tested for total oxidation of CO and C3H8. The activity of the fresh PLA catalysts for CO and C3H8 oxidation increased with increasing calcination temperature of the support, while the activities of the aged catalysts declined and became essentially the same. CO chemisorption results revealed that the suppressed activities of the aged catalysts were mainly due to the decline of palladium dispersion. The turnover frequency（TOF） of CO oxidation increased with increasing reduction ability of the catalysts, with a fresh catalyst calcined at 1050 oC having the highest value（0.048 s–1）. However, the TOF of C3H8 total oxidation was affected by not only the redox properties of catalysts but also the size of Pd particle, and large Pd particles possessed higher TOF value of C3H8 oxidation, with the highest value（0.125 s–1） being obtained on an aged catalyst calcined at 500 oC.