Model Catalysts Research Articles

The Surface Chemistry of Methanol on Pd(111) and H-Pd(111) Surfaces: C-O Bond Cleavage and the Effects of Metal Hydride Formation.

Palladium catalysts are frequently employed in processes where methanol is an energy vector or carrier, being useful for the synthesis of methanol from mixtures of carbon dioxide and hydrogen (CO2/H2) or its steam reforming on demand. Results of synchrotron-based ambient pressure X-ray photoelectron spectroscopy for the adsorption of methanol on a Pd(111) model catalyst show a rich surface chemistry and complex phenomena that strongly depend on pressure and temperature. At low pressures (<10-6 Torr) and temperatures (<300 K), CO is the dominant decomposition product. As the pressure increases, cleavage of C-H, O-H, and C-O bonds is observed, and at elevated temperatures (400-600 K) the formation of CO and CHx/C fragments compete on the surface. Thus, existing reaction networks for methanol decomposition must be modified. Furthermore, surface and subsurface hydrogen (coming from PdHx) play a significant role in the stability and removal of CHx and C species.

Insight into the performance-boosting mechanism of Ag/MgAlOx for NH3 selective catalytic oxidation: Perspective from the support crystalline phase structures

Arranging an ammonia oxidation process after the selective catalytic reduction of NOx by NH3 (NH3-SCR) system is an effective way for ensuring the DeNOx efficiency and controlling the slip ammonia. To improve operability and reduce operating costs in ammonia selective catalytic oxidation (NH3-SCO), developing feasible and efficient catalysts becomes meaningful. Herein, focusing on the dilemma of Ag/Al2O3 catalysts in NH3-SCO applications, Ag/MgAlOx catalysts with different support different crystalline phase structures (5 %Ag/MgAl-LDO and 5 %Ag/MgAl2O4) were innovatively synthesized and systematically evaluated application potential in NH3-SCO. Results indicated that the introduction of Mg apparently broadened reaction temperature window and catalytic performance of 5 %Ag/MgAl2O4 was higher than 5 %Ag/MgAl-LDO, while the N2 selectivity was completely opposite. The combination of series characterization and density functional theory (DFT) calculations revealed that 5 %Ag/MgAl2O4 surface has more Ag0 species with small particle size, which is favorable for ammonia adsorption and activated dehydrogenation to further promote reaction of NOx species, resulting in a higher NH3-SCO activity. In contrast, 5 %Ag/MgAl-LDO readily induces oxidized Ag species and Ag0 is more inclined to be present in large particle sizes, which is more conducive to dissociation of O2 to produce reactive O species (O*) leading to the peroxidation of ammonia to nitrate and thus, positively affects the improvement of N2 selectivity. Model catalyst 5 %Ag/MgAl-650 (mixed-phase) was prepared by controlling the roasting conditions and exhibited excellent catalytic performance in NH3-SCO with almost 93 % of NH3 oxidized at 250 °C (N2 selectivity up to 71 %). This work could afford theoretical support for the optimization and application of catalysts with high performance at low temperatures in selective catalytic oxidation of slip ammonia.

EFFECT OF THE FEED GAS MIXTURE COMPOSITION AT METHANOL DEHYDROGENATION TO FORMALDEHYDE ON SUPPORTED OXIDE CATALYSTS

The article presents the results of a study of the activity of deposited oxide catalysts in the process of obtaining formaldehyde from methanol. Model catalysts were prepared by impregnation of finely porous silica gel with nitrate solutions of zinc, copper, silver, sodium, followed by heat treatment. The catalytic properties of the samples were studied in the reaction of methanol dehydrogenation in the flow mode on a fine fraction of the catalyst. With the complication of the composition of the feed gas mixture, part of argon was replaced with hydrogen, mono- and carbon dioxide. The reaction mixture was analyzed by gas chromatography, IR spectroscopy and photocolorimetry. At a temperature of ~350 °C, a noticeable formation of formaldehyde begins, upon reaching a temperature of 500 °C in the reactor, methanol processing begins to decrease, while the concentration of formaldehyde changes insignificantly. Along with formaldehyde, dimethyl ether, methane and carbon dioxide are fixed in the reaction products. At the end of the tests on the surface of the catalyst, carbon, oxygen and hydrogen are quantified using elemental analysis methods, the ratio between which corresponds to the formula (-COH-)n. That is, along with the target reaction, methanol is consumed for the formation of surface hydrocarbons. Oxymethylene oligomers can decompose along two competing routes to form formaldehyde or carbon and CO2. The addition of carbon dioxide to the feed gas mixture after the catalyst enters the stationary mode leads to a significant increase in its formaldehyde yield. It is obvious that the route with the formation of carbon dioxide is associated with the target reaction of formaldehyde production, where the catalytic reaction maintains a certain concentration of active centers. Thus, it can be assumed that carbon dioxide as a product of decomposition of surface oxymethylene compounds affects the rate of the catalytic reaction by maintaining a certain concentration of surface hydrocarbons, which are necessary as an element of the active catalytic center. For citation: Morozov L.N., Vorobyov A.S., Kunin A.V., Egorov N.A., Timoshin E.S. Effect of the feed gas mixture composition at methanol dehydrogenation to formaldehyde on supported oxide catalysts. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 7. P. 88-95. DOI: 10.6060/ivkkt.20246707.7003.

Spectroscopic Investigations of Complex Electronic Interactions by Elemental Doping and Material Compositing of Cobalt Oxide for Enhanced Oxygen Evolution Reaction Activity

AbstractDoping and compositing are two universal design strategies used to engineer the electronic state of a material and mitigate its disadvantages. These two strategies are extensively applied to design efficient electrocatalysts for water splitting. Using cobalt oxide (CoO) as a model catalyst, it is proven that the oxygen evolution reaction (OER) performance can be progressively improved, first by Fe‐doping to form Fe‐CoO solid solution, and further by the addition of CeO2 to produce a Fe‐CoO/CeO2 composite. X‐ray absorption spectroscopy (XAS) reveals that distinct electronic interactions are induced by the processes of doping and compositing. Fe‐doping of CoO can break down the structural symmetry, changing the electronic structure of both Co and O species at the surface and decreasing the flat‐band potential (Vfb). In comparison, subsequent compositing of Fe‐CoO with CeO2 induces negligible electronic changes in the Fe‐CoO (as seen in ex situ characterizations), but significantly modifies the oxidative transformations of both Co and Fe under OER conditions. The spectroscopic investigations reveal that Fe‐doping and CeO2 compositing play different roles in modifying the electronic properties of CoO in its pristine state and during OER catalysis, in return, providing useful guidance for the design of more efficient electrocatalysts using these two strategies.

Recent progress in understanding the nature of active sites for methanol synthesis over Cu/ZnO catalysts

Copper-zinc-alumina (Cu/ZnO/Al2O3) has been utilized as the leading catalyst for industrial methanol synthesis via hydrogenation of CO and CO2 for more than 50 years. Understanding the nature of active Zn sites at the atomic level is vital for gaining insight into the reaction mechanism and rational design of more efficient Cu/ZnO catalysts for methanol synthesis but remains greatly challenging and has been intensively debated for decades. In this mini-review, we first describe the fundamental insights obtained from well-defined model catalysts and then summarize the recent experimental evidence with respect to dynamic structural and electronic changes in the active Zn phase under realistic working conditions by in situ/operando microscopy/spectroscopy and surface site titration using probing molecules. In the following, we discuss the catalytic mechanism of diverse active structures by theoretical calculations and simulations. Therefore, the critical role of interfacial sites between metallic Cu and ZnO, especially those with oxygen defects, in methanol synthesis via CO2 hydrogenation is emphasized. Finally, we discuss the technical challenges and perspectives in understanding the origins of this Cu-ZnO synergy and rational design of next-generation Cu-based methanol synthesis catalysts.

Precise structure-tailoring of multicomponent nanocatalysts enabled by continuous flow-controlled flash nanoprecipitation technique

Nanostructured catalysts with diverse compositions offer an exciting prospect for various catalytic applications. The precise control of nanostructures allows to tune the physicochemical properties of nanocatalysts and improve their performance. However, most preparative methods rely on conventional batch systems, which require tedious procedures and cause low productivity. Herein, we reported a novel engineered flash nanoprecipitation (FNP) technique to synthesize well-structured nanocatalysts in a continuous-flow procedure with intelligent operation and high productivity, in which a series of multicomponent bismuth oxyhalides (BiOClxBr1-x) were demonstrated as the model catalysts. This method was established on the uninterrupted continuous synthesis of BiOClxBr1-x with precisely controlled microstructure by simply altering the flow rate ratio of precursor fluids in the reactor. The computational fluid dynamics (CFD) simulation showed that the automized flow setup could achieve the accurate control over the intensified fluid mixing. Significantly, a volcano relationship between the halogen compositions and catalytic activities toward photodegradation of tetracycline (TC) was observed, which indicated that the structural changes enabled band structure-dependent regulation. The FNP-processed BiOCl0.75Br0.25 possessed a balanced redox ability and light absorption, thus located at the peak of volcano with a five-fold enhancement of intrinsic photocatalytic activity. Overall, this work provides a promising prospect of continuous-flow technique in the engineered manufacturing of the advanced nanomaterials, offering fine-tuning of the nanostructures of materials with low cost and high productivity.

Interface Effects in the Stability of 2D Silica, Silicide, and Silicene on Pt(111) and Rh(111).

Ultrathin two-dimensional silica films have been suggested as highly defined conductive models for fundamental studies on silica-supported catalyst particles. Key requirements in this context are closed silica films that isolate the gas phase from the underlying metal substrate and stability under reaction conditions. Here, we present silica bilayer films grown on Pt(111) and Rh(111) and characterize them by scanning tunneling microscopy and X-ray photoelectron spectroscopy. We provide the first report of silica bilayer films on Rh(111) and have further successfully prepared fully closed films on Pt(111). Interestingly, surface and interface silicide phases play a decisive role in both cases: On platinum, closed films can be stabilized only when silicon is deposited in excess, which results in an interfacial silicide or silicate layer. We show that these silica films can also be grown directly from a surface silicide phase. In the case of rhodium, the silica phase is less stable and can be reduced to a silicide in reductive environments. Though similar in appearance to the "silicene" phases that have been controversially discussed on Ag(111), we conclude that an interpretation of the phase as a surface silicide is more consistent with our data. Finally, we show that the silica film on platinum is stable in 0.8 mbar CO but unstable at elevated temperatures. We thus conclude that these systems are only suitable as model catalyst supports to a limited extent.

Synergistic M‐O Dual‐Atom Pairs Induced Interfacial Water Hydrogen Bonding Network for Boosting MoSe2 Electrocatalytic Performance

AbstractUnderstanding the dynamics changes of the water network at the electrode–solution interface during the hydrogen evolution reaction (HER) process, including how it is doubly regulated by the electrode material and electrolyte pH, and its subsequent effects on the reaction intermediates (H* and OH*), is crucial in electrochemistry. However, relevant studies are limited due to water's its dual role as both a reactant and a solvent. Thus, it is essential to construct an ideal model capable of decoupling the effects of interfacial water action from the surface catalytic HER process. In this study, M‐O atom pairs doped MoSe2 model catalyst is developed to achieve this goal and tailor the water network structure in a double‐layer microenvironment. Combined with molecular dynamics simulations and in situ spectroscopic characterization, correlations between water configuration, the water network, and water dissociation with HER activity are successfully established. This findings reveal that the pH‐dependent hydrogen‐bonding environment, modulated by oxophilic species, exerts a greater influence on acidic HER compared to alkaline media. The optimized Rh,O‐MoSe2‐x catalyst demonstrates exceptional performance in both acid and alkaline electrolytes and shows no activity decay during a PEMWE test at 1.5 A cm−2, making it promising for scalable water electrolyzers.

Stepwise structural evolution toward robust carboranealkynyl-protected copper nanocluster catalysts for nitrate electroreduction.

Atomically precise metal nanoclusters (NCs) are emerging as idealized model catalysts for imprecise metal nanoparticles to unveil their structure-activity relationship. However, the directional synthesis of robust metal NCs with accessible catalytic active sites remains a great challenge. In this work, we achieved bulky carboranealkynyl-protected copper NCs, the monomer Cu13·3PF6 and nido-carboranealkynyl bridged dimer Cu26·4PF6, with fair stability as well as accessible open metal sites step by step through external ligand shell modification and metal-core evolution. Both Cu13·3PF6 and Cu26·4PF6 demonstrate remarkable catalytic activity and selectivity in electrocatalytic nitrate (NO3-) reduction to NH3 reaction, with the dimer Cu26·4PF6 displaying superior performance. The mechanism of this catalytic reaction was elucidated through theoretical computations in conjunction with in situ FTIR spectra. This study not only provides strategies for accessing desired copper NC catalysts but also establishes a platform to uncover the structure-activity relationship of copper NCs.

Insight into the size-dependent activity in Ag/SiO2 catalyzed hydrogenation of dimethyl oxalate to methyl glycolate

Methyl glycolate (MG) is an important building block for synthesizing biodegradable material of polyglycolic acid. Hydrogenation of coal-based dimethyl oxalate (DMO) to MG is quite promising, where Ag-based catalysts exhibited excellent selectivity. Here, a series of Ag/SiO2-x catalysts with particle sizes of 1.4–13.5 nm were prepared, which showed significant structural sensitivity in DMO hydrogenation. For Ag nanoparticles of 1.4–2.7 nm, the turnover frequency (TOF) was linearly increased with the surface electron density of silver, but when the Ag nanoparticles further enlarged, no significant variation of TOF was observed. Combining DFT calculation and experimental results of the model catalyst, triangular nanoplate, it was deduced that the Ag (111) played a dominant role in DMO hydrogenation to MG, originating from the benefited MG desorption as well as promoted dissociation of H2 and DMO. This understanding about Ag particle size effect may provide guidance for designing efficient catalysts for DMO hydrogenation to MG.

Tailoring atomic chemistry to refine reaction pathway for the most enhancement by magnetization in water oxidation

Water oxidation on magnetic catalysts has generated significant interest due to the spin-polarization effect. Recent studies have revealed that the disappearance of magnetic domain wall upon magnetization is responsible for the observed oxygen evolution reaction (OER) enhancement. However, an atomic picture of the reaction pathway remains unclear, i.e., which reaction pathway benefits most from spin-polarization, the adsorbent evolution mechanism, the intermolecular mechanism (I2M), the lattice oxygen-mediated one, or more? Here, using three model catalysts with distinguished atomic chemistries of active sites, we are able to reveal the atomic-level mechanism. We found that spin-polarized OER mainly occurs at interconnected active sites, which favors direct coupling of neighboring ligand oxygens (I2M). Furthermore, our study reveals the crucial role of lattice oxygen participation in spin-polarized OER, significantly facilitating the coupling kinetics of neighboring oxygen radicals at active sites.

Enhancing Oxygen Evolution Reaction with Two-Dimensional Nickel Oxide on Au (111)

The nature of the active sites of transition metal oxides during the oxygen evolution reaction (OER) has attracted much attention. Herein, we constructed well-defined nickel oxide/Au (111) model catalysts to study the relationship between the structures and their OER activity using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), electrochemical measurements, and density functional theory (DFT) calculations. The deposited nickel oxides on Au (111) were found to exhibit a two-dimensional (2D)/three-dimensional (3D) structure by regulating the annealing temperature. Combining STM, XPS and electrochemical measurements, our results demonstrated an optimal OER reactivity could be achieved for NiOx with a 2D structure on Au and provided a morphological description of the active phase during electrocatalysis.

Functional Improvement of NiOx/CeO2 Model Catalyst Active in Dry Methane Reforming via Optimization of Nickel Content

The valorization of greenhouse gases, especially when focused on carbon dioxide, currently belongs to the main challenges of pro-environmental chemical processes. One of the important technologies in this field is dry methane reforming (DMR), leading to the so-called synthesis gas (CO + H2). However, to be efficient and economically viable, an active and stable catalyst is required. Ni-based systems can be recommended in this regard. This research aimed to investigate how nickel content can influence the activity of model NiOx/CeO2 catalysts in DMR. A series of NiOx/CeO2 samples of various nickel loadings (0–10 wt.%) were prepared through dry impregnation. The obtained samples were characterized through XRD, RS, N2-BET, DRIFT, SEM, UV/Vis-DR, and XPS. Nonlinear changes in surface properties of the investigated samples with increasing nickel concentration were found. The observed changes are mirrored both in the determined nickel speciation and in the corresponding catalytic activity. The highest activity was found for the catalyst containing 3 wt.%. of nickel.

Surface Coordination Environment Engineering on PtxCu1-x Alloy Catalysts for the Efficient Photocatalytic Reduction of CO2 to CH4.

Alloy catalysts have been reported to be robust in catalyzing various heterogeneous reactions due to the synergistic effect between different metal atoms. In this work, aimed at understanding the effect of the coordination environment of surface atoms on the catalytic performance of alloy catalysts, a series of PtxCu1-x alloy model catalysts supported on anatase-phase TiO2 (PtxCu1-x/Ti, x = 0.4, 0.5, 0.6, 0.8) were developed and applied in the classic photocatalytic CO2 reduction reaction. According to the results of catalytic performance evaluation, it was found that the photocatalytic CO2 reduction activity on PtxCu1-x/Ti showed a volcanic change as a function of the Pt/Cu ratio, the highest CO2 conversion was achieved on Pt0.5Cu0.5/Ti, with CH4 as the main product. Further systematic characterizations and theoretical calculations revealed that the equimolar amounts of Pt and Cu in Pt0.5Cu0.5/Ti facilitated the generation of more Cu-Pt-paired sites (i.e., the higher coordination number of Pt-Cu), which would favor a bridge adsorption configuration of CO2 and facilitate the electron transfer, thus resulting in the highest photocatalytic CO2 reduction efficiency on Pt0.5Cu0.5/Ti. This work provided new insights into the design of excellent CO2 reduction photocatalysts with high CH4 selectivity from the perspective of surface coordination environment engineering on alloy catalysts.

Enzyme-Inspired Ligand Engineering of Gold Nanoclusters for Electrocatalytic Microenvironment Manipulation.

Natural enzymes intricately regulate substrate accessibility through specific amino acid sequences and folded structures at their active sites. Achieving such precise control over the microenvironment has proven to be challenging in nanocatalysis, especially in the realm of ligand-stabilized metal nanoparticles. Here, we use atomically precise metal nanoclusters (NCs) as model catalysts to demonstrate an effective ligand engineering strategy to control the local concentration of CO2 on the surface of gold (Au) NCs during electrocatalytic CO2 reduction reactions (CO2RR). The precise incorporation of two 2-thiouracil-5-carboxylic acid (TCA) ligands within the pocket-like cavity of [Au25(pMBA)18]- NCs (pMBA = para-mercaptobenzoic acid) leads to a substantial acceleration in the reaction kinetics of CO2RR. This enhancement is attributed to a more favorable microenvironment in proximity to the active site for CO2, facilitated by supramolecular interactions between the nucleophilic Nδ- of the pyrimidine ring of the TCA ligand and the electrophilic Cδ+ of CO2. A comprehensive investigation employing absorption spectroscopy, mass spectrometry, isotopic labeling measurements, electrochemical analyses, and quantum chemical computation highlights the pivotal role of local CO2 enrichment in enhancing the activity and selectivity of TCA-modified Au25 NCs for CO2RR. Notably, a high Faradaic efficiency of 98.6% toward CO has been achieved. The surface engineering approach and catalytic fundamentals elucidated in this study provide a systematic foundation for the molecular-level design of metal-based electrocatalysts.

Collaborative optimization of de-NOx & NH4HSO4 decomposition over Cu-based LDO catalysts: Perspective from the acidic and redox properties

Low temperature de-NOx catalyst with excellent resistance to ammonium bisulfate (ABS) is of great practical significance. Study about the simultaneous optimization of de-NOx performance and ABS resistance by acidic and redox properties regulation is imperative. In this work, the influence of the acidic and redox properties to the de-NOx & ABS decomposition performance was investigated via three Cu-based LDO model catalysts with distinct surface chemical character. Test results indicated that the low temperature de-NOx performance of both the modified Cu2NiAl-LDO and Cu2CoAl-LDO catalysts was slightly improved, while their in situ ABS resistance behavior was remarkably different (Cu2CoAl-LDO > Cu3Al-LDO > Cu2NiAl-LDO). TPDC and TPSR test evidenced that the ABS thermal decomposition or its reactivity with NOx was facilitated over Cu2CoAl-LDO catalyst, but inhibited over Cu2NiAl-LDO catalyst. Characterizations revealed the Cu2CoAl-LDO catalyst with stronger redox property could contribute to ABS decomposition, while more weak acid sites on Cu2NiAl-LDO catalyst induced a negative effect for ABS decomposition. Our study might provide guidance on the rational design of de-NOx & anti-ABS catalysts for future studies.

Regulation of the d-band center of metal–organic frameworks for energy-saving hydrogen generation coupled with selective glycerol oxidation

The hybrid electrolyzer coupled glycerol oxidation (GOR) with hydrogen evolution reaction (HER) is fascinating to simultaneously generate H2 and high value-added chemicals with low energy input, yet facing a challenge. Herein, Cu-based metal-organic frameworks (Cu-MOFs) are reported as model catalysts for both HER and GOR through doping of atomically dispersed precious and nonprecious metals. Remarkably, the HER activity of Ru-doped Cu-MOF outperformed a Pt/C catalyst, with its Faradaic efficiency for formate formation at 90% at a low potential of 1.40 V. Furthermore, the hybrid electrolyzer only needed 1.36 V to achieve 10 mA cm-2, 340 mV lower than that for splitting pure water. Theoretical calculations demonstrated that electronic interactions between the host and guest (doped) metals shifted downward the d-band centers (εd) of MOFs. This consequently lowered water adsorption and dissociation energy barriers and optimized hydrogen adsorption energy, leading to significantly enhanced HER activities. Meanwhile, the downshift of εd centers reduced energy barriers for rate-limiting step and the formation energy of OH*, synergistically enhancing the activity of MOFs for GOR. These findings offered an effective means for simultaneous productions of hydrogen fuel and high value-added chemicals using one hybrid electrolyzer with low energy input.

Nitrogen-doped MoO2/Cu heterojunction electrocatalyst for highly efficient alkaline hydrogen evolution reaction

Metal/metal-(hydr)oxide heterojunction has been proposed as an efficient means to enhance the kinetics of alkaline hydrogen evolution reaction (HER). However, the poor electronic conductivity of metal-(hydr)oxides hinders the transport of electrons and the inappropriate electronic structure of the constituent phases would lower the HER activity. Herein, a nitrogen-doped MoO2/Cu heterostructure nanosheets was prepared by a simple hydrothermal and subsequent annealing treatment, acting as a model catalyst for element-doped modified metals/metal-oxides composite towards alkaline HER. Experimental results revealed that the HER catalytic activity of the catalyst was effectively improved by the nitrogen doping and the hetero coupling effect. The obtained N–MoO2/Cu catalyst exhibited a low overpotential of 40 and 363 mV to drive the current densities of 10 and 1000 mA cm−2, respectively, and showed high stability in the constant-current test of 50 h at 10 mA cm−2, 100 mA cm−2 and 1000 mA cm−2. Impressively, the N–MoO2/Cu catalyst coupled with Ni–Fe LDH to assemble an alkaline electrolyzer only require a voltage of 1.49 V to achieve a current density of 10 mA cm−2, and could be actuated by wind power to continuously produce hydrogen.

A Critical View on the Quantification of Model Catalyst Activity

The conversion of reactants, reaction rate referred to catalyst mass, and turnover frequency (TOF) are values typically employed to compare the activity of different catalysts. However, experimental parameters have to be chosen carefully when systems of different complexity are compared. In order to characterize UHV-based model systems, we use a highly sensitive sniffer setup which allows us to investigate the catalytic activity by combining three different measurement modes: temperature-programmed desorption, continuous flow, and pulsed-reactivity experiments. In this article, we explore the caveats of quantifying catalytic activity in UHV on the well-studied and highly defined reference system of CO oxidation on Pt(111), which we later compare to the same reaction on Pt19 clusters deposited on Fe3O4(001). We demonstrate that we can apply fast heating ramps for TOF quantification, thus inducing as little sintering as possible in the metastable clusters. By changing the reactant ratio, we find transient reactivity effects that influence the TOF, which should be kept in mind when comparing catalysts. In addition, the TOF also depends on the surface coverage that itself is a function of temperature and pressure. At a constant reactant ratio, in the absence of transient effects, however, the TOF scales linearly with total pressure over the entire measured temperature range from 200 to 700 K since the reaction rate is dependent on both reactant partial pressures with temperature-dependent reaction order. When comparing the maximum TOF at this particular reactant ratio, we find a 1.6 times higher maximum TOF for Pt19/Fe3O4(001) than for Pt(111). In addition, pulsed-reactivity measurements help identify purely reaction-limited regimes and allow for a more detailed investigation of limiting reactants over the whole temperature range.

Identifying Electrocatalytic Activity Sequence of Metal Phthalocyanines for the Hydrogen Peroxide Oxidation Reaction

The hydrogen peroxide oxidation reaction (HPOR) plays a vital role in the emerging H2-H2O2 cycle energy storage system, in which the rational design of HPOR electrocatalyst is essential for achieving high system efficiency. Herein, we establish the HPOR activity trends using structurally well-defined metal phthalocyanines (MPc) as model catalysts via a combined experimental and computational approach. The measured activity sequence follows the order of CoPc > FePc > MnPc > ZnPc > H2Pc > NiPc > CuPc based on their site-normalized exchange current (i 0-s). Theoretical calculations indicate that the binding free energy of hydroperoxyl intermediate, HOO*, on MPc (ΔG HOO*) is the activity descriptor for HPOR. A volcano-type activity trend is observed by correlating the logarithm of i 0-s (logi 0-s) with the ΔG HOO* values and agrees with the theoretical predictions. This HPOR activity trend provides insights into the design of highly active electrocatalysts for HPOR and related energy applications.