Stability of dimensionally stable anode for chlorine evolution reaction

Chlorine(Cl2)is one of the most important chemicals produced by the electrolysis of brine solutions and is a key raw material for many areas of industrial chemistry.For nearly half a century,dimensionally stable anode(DSA)made from a mixture of RuO_(2) and TiO_(2) solid oxides coated on Ti substrate has been the most widely used electrode for chlorine evolution reaction(CER).In harsh operating environments,the stability of DSAs remains a major challenge greatly affecting their lifetime.The deactivation of DSAs significantly increases the cost of the chlor-alkali industry due to the corrosion of Ru and the formation of the passivation layer TiO_(2).Therefore,it is urgent to develop catalysts with higher activity and stability,which requires a thorough understanding of the deactivation mechanism of DSA catalysts.This paper reviews existing references on the deactivation mechanisms of DSA catalysts,including both experimental and theoretical studies.Studies on how CER selectivity affects electrode stability are also discussed.Furthermore,studies on the effects of the preparation process,elemental composition,and surface/interface structures on the DSA stability and corresponding improvement strategies are summarized.The development of other non-DSA-type catalysts with comparable stability is also reviewed,and future opportunities in this exciting field are also outlined.

Surface engineering of 1D nanocatalysts for value-added selective electrooxidation of organic chemicals

Electrolytic water splitting by renewable energy is a technology with great potential for producing hydrogen(H_(2))without carbon emission,but this technical route is hindered by its huge energy(electricity)cost,which is mainly wasted by the anode oxygen evolution reaction(OER)while the value of the anode product(oxygen)is very limited.Replacing the high-energy-cost OER with a selective organic compound electrooxidation carried out at a relatively lower potential can reduce the electricity cost while producing value-added chemicals.Currently,H_(2) generation coupled with synthesis of value-added organic compounds faces the challenge of low selectivity and slow generation rate of the anodic products.One-dimensional(1D)nanocatalysts with a unique morphology,well-defined active sites,and good electron conductivity have shown excellent performance in many electrocatalytic reactions.The rational design and regulation of 1D nanocatalysts through surface engineering can optimize the adsorption energy of intermediate molecules and improve the selectivity of organic electrooxidation reactions.Herein,we summarized the recent research progress of 1D nanocatalysts applied in different organic electrooxidation reactions and introduced several different fabrication strategies for surface engineering of 1D nanocatalysts.Then,we focused on the relationship between surface engineering and the selectivity of organic electrooxidation reaction products.Finally,future challenges and development prospects of 1D nanocatalysts in the coupled system consisting of organic electrooxidation and hydrogen evolution reactions are briefly outlined.

Improving hydrogen evolution reaction efficiency through lattice tuning

The intermittent nature of renewable energy sources sets a requirement for efficient energy storage to mitigate the conflict between energy supply and demand.Hydrogen is a promising choice for energy storage due to its high energy density.However,the conversion of electrical energy to chemical energy stored in hydrogen through water electrolysis suffers from low efficiency,and the electricity cost dominates the total cost of hydrogen production.Here,we report the study of improving the hydrogen evolution reaction activity of Pt-based catalysts by building a nanoscale surface NiO and Pt interface,further optimizing the performance via tuning the lattice parameter of the core of nanoparticles,which can be achieved by varying the dealloying annealing time.The optimized PtCuNi-O/C and PtNi-O/C catalysts are demonstrated to be one of the best catalysts,with a mass activity(MA)of 9.1 and 8.7 mA/μgPt,which is 9.9-fold and 9.5-fold of that of Pt/C,respectively.

The Active Sites and Corresponding Stability Challenges of the M-N-C Catalysts for Proton Exchange Membrane Fuel Cell

Proton exchange membrane fuel cells(PEMFCs)as promising alternatives to traditional internal combustion engines have attracted massive concerns to promote their wide application in society.However,the biggest challenge to the commercialization of PEMFCs remains the high cost due to the adoption of the platinum group metal(PGM)catalysts in the cathode.

Pt3Ag alloy wavy nanowires as highly effective electrocatalysts for ethanol oxidation reaction

Direct ethanol fuel cell(DEFC)has received tremendous research interests because of the more convenient storage and transportation of ethanol vs.compressed hydrogen.However,the electrocatalytic ethanol oxidation reaction typically requires precious metal catalysts and is plagued with relatively high over potential and low mass activity.Here we report the synthesis of Pt3Ag alloy wavy nanowires via a particle attachment mechanism in a facile solvothermal process.Transmission microscopy studies and elemental analyses show highly wavy nanowire structures with an average diameter of 4.6±1.0 nm and uniform Pt3Ag alloy formation.Electrocatalytic studies demonstrate that the resulting alloy nanowires can function as highly effective electrocatalysts for ethanol oxidation reactions(EOR)with ultrahigh specific activity of 28.0 mA/cm^2 and mass activity of 6.1 A/mg,far exceeding that of the commercial Pt/carbon samples(1.10 A/mg).The improved electrocatalytic activity may be partly attributed to partial electron transfer from Ag to Pt in the Pt3Ag alloy,which weakens CO binding and the CO poisoning effect.The one-dimensional nanowire morphology also contributes to favorable charge transport properties that are critical for extracting charge from catalytic active sites to external circuits.The chronoamperometry studies demonstrate considerably improved stability for long term operation compared with the commercial Pt/C samples,making the Pt3Ag wavy nanowires an attractive electrocatalyst for EOR.

Ultrathin wavy Rh nanowires as highly effective electrocatalysts for methanol oxidation reaction with ultrahigh ECSA

Direct methanol fuel cells (DMFCs) have received tremendous research interests because of the facile storage of liquid methanol vs.hydrogen.However,the DMFC today is severely plagued by the poor kinetics and rather high overpotential in methanol oxidation reaction (MOR).Here we report the investigation of the ultrathin Rh wavy nanowires as a highly effective MOR electrocatalyst.We show that ultrathin wavy Rh nanowires can be robustly synthesized with 2-3 nm diameters.Electrochemical studies show a current peak at the potential of 0.61 V vs.reversible hydrogen electrode (RHE),considerably lower than that of Pt based catalysts (~ 0.8-0.9 V vs.RHE).Importantly,with ultrathin diameters and favorable charge transport,the Rh nanowires catalysts exhibit an ultrahigh electrochemically active surface area determined from CO-stripping (ECSAco) of 144.2 m2/g,far exceeding that of the commercial Rh black samples (20 m2/g).Together,the Rh nanowire catalysts deliver a mass activity of 722 mA/mg at 0.61 V,considerably higher than many previously reported electrocatalysts at the same potential.The chronoamperometry studies also demonstrate good stability and CO-tolerance compared with the Rh black control sample,making ultrathin Rh wavy nanowires an attractive electrocatalyst for MOR.

In situ development of highly concave and compositionconfined PtNi octahedra with high oxygen reduction reaction activity and durability

Controlled syntheses of PtNi metal nanocrystals with unique structures for catalyzing oxygen reduction reactions （ORRs） have attracted great interest. Here, we report the one-step synthesis of single-crystal PtNi octahedra with in situ-developed highly concave features and self-confined composition that are optimal for ORR. Detailed studies revealed that the Pt-rich seeding, subsequent Pt/Ni co-reduction, and Pt-Ni interfusion resulted in uniform single-crystal PtNi octahedra, and that the combination of Ni facet segregation and oxygen etching of a Ni-rich surface led to the concavity and confined Ni content. The concave PtNi nanocrystals exhibited much higher ORR performance than the commercially available Pt/C catalyst in terms of both specific activity （29.1 times higher） and mass activity （12.9 times higher） at 0.9 V （vs. reversible hydrogen electrode （RHE））. The performance was also higher than that of PtNi octahedra without concavity, confirming that the higher activity was closely related to its morphology. Moreover, the concave octahedra also exhibited remarkable stability in ORR （93% mass activity remained after 10,000 cycles between 0.6 and 1.1 V vs. RHE） owing to the passivation of the unstable sites.

1D PtCo nanowires as catalysts for PEMFCs with low Pt loading

The high cost of platinum(Pt)-group metal(PGM)-based catalysts used in proton-exchange membrane fuel cells(PEMFCs)poses a critical roadblock to their widespread adoption.Although using low PGM loading PEMFCs can largely address this challenge,high current density performance will be severely compromised consequently.To overcome this dilemma,we report the development of ultrathin platinum-cobalt nanowires(PtCoNWs)as the cathode catalysts for ultralow Pt loading and high-performance membrane electrode assembly(MEA).The Pt Co NWs delivered a record-high mass activity(MA)of 1.06±0.14 A mg_(Pt)^(-1) of Pt-alloy catalysts towards oxygen reduction reaction(ORR)in MEA,yielding an impressive total Pt utilization of 5.14 W_(rate)mg_(Pt)^(-1).The PtCoNWs retained a respectable endof-life MA of 0.45 Amg_(Pt)^(-1) after the 30,000 cycles square-wave accelerated stability test,which is still above the Department of Energy 2020 beginning-of-life target for catalysts.In-situ Xray absorption spectroscopy studies suggest that the high degree of alloying in the Pt Co NWs stabilizes the ultrathin structure and may contribute to the high ORR activity and power density performance in PEMFC.

Synthesis of surface controlled nickel/palladium hydride nanodendrites with high performance in benzyl alcohol oxidation

Benzaldehyde byproduct is an imperative intermediate in the production of fine chemicals and additives.Tuning selectivity to benzaldehyde is therefore critical in alcohol oxidation reactions at the industrial level.Herein,we report a simple but innovative method for the synthesis of palladium hydride and nickel palladium hydride nanodendrites with controllable morphology,high stability,and excellent catalytic activity.The synthesized dendrites can maintain the palladium hydride phase even after their use in the chosen catalytic reaction.Remarkably,the high surface area morphology and unique interaction between nickel-rich surface and palladium hydride (β-phase) of these nanodendrites are translated in an enhanced catalytic activity for benzyl alcohol oxidation reaction.Our Ni/PdH0.43 nanodendrites demonstrated a high selectivity towards benzaldehyde of about 92.0% with a conversion rate of 95.4%,showing higher catalytic selectivity than their PdH0.43 counterparts and commercial Pd/C.The present study opens the door for further exploration of metal/metal-hydride nanostructures as next-generation catalytic materials.