Surface Structure Of Catalysts Research Articles

Facet-Dependent Surface Restructuring on Nickel (Oxy)hydroxides: A Self-Activation Process for Enhanced Oxygen Evolution Reaction.

Unraveling the catalyst surface structure and behavior during reactions is essential for both mechanistic understanding and performance optimization. Here we report a phenomenon of facet-dependent surface restructuring intrinsic to β-Ni(OH)2 catalysts during oxygen evolution reaction (OER), discovered by the correlative ex situ and operando characterization. The ex situ study after OER reveals β-Ni(OH)2 restructuring at the edge facets to form nanoporous Ni1-xO, which is Ni deficient containing Ni3+ species. Operando liquid transmission electron microscopy (TEM) and Raman spectroscopy further identify the active role of the intermediate β-NiOOH phase in both the OER catalysis and Ni1-xO formation, pinpointing the complete surface restructuring pathway. Such surface restructuring is shown to effectively increase the exposed active sites, accelerate Ni oxidation kinetics, and optimize *OH intermediate bonding energy toward fast OER kinetics, which leads to an extraordinary activity enhancement of ∼16-fold. Facilitated by such a self-activation process, the specially prepared β-Ni(OH)2 with larger edge facets exhibits a 470-fold current enhancement than that of the benchmark IrO2, demonstrating a promising way to optimize metal-(oxy)hydroxide-based catalysts.

A Review of the Structure–Property Relationship of Nickel Phosphides in Hydrogen Production

Hydrogen, one of the most promising forms of new energy sources, due to its high energy density, low emissions, and potential to decarbonize various sectors, has attracted significant research attention. It is known that electrocatalytic hydrogen production is one of the most widely investigated research directions due to its high efficiency in the conversion of electricity to H2 gas. However, given the limited reserves and high cost of precious metals, the search for non-precious metal-based catalysts has been widely explored, for example, transition metal phosphides, oxides, and sulfides. Despite this interest, a detailed survey unveils that the surface and internal structures of the alternative catalysts, including their surface reconstruction, composition, and electronic structure, are poorly studied. As a result, a disconnection in the structure–property relationship severely hinders the rational design of efficient and reliable non-precious metal-based catalysts. In this review, by focusing on Ni5P4, a bifunctional catalyst for water splitting, we systematically summarize the material motifs pertaining to the different synthetic methods, surface characteristics, and hydrolysis properties. It is believed that a cascaded correlation may provide insights toward understanding the fundamental catalytic mechanism and design of robust alternative catalysts for hydrogen production.

Ethane Dehydrogenation to Ethylene: Engineering the Surface Structure of Pt-Based Alloy Catalysts to Tune the Catalytic Performance

Ethane Dehydrogenation to Ethylene: Engineering the Surface Structure of Pt-Based Alloy Catalysts to Tune the Catalytic Performance

Dealloying Strategies for Mesoporous AuCu Nanoparticles: Impact on Internal Metallic Structure and Electrocatalytic Performance

Tailoring the surface structure of the mesoporous metal catalysts is pivotal for influencing both the catalytic activity and selectivity. Through the dealloying of bimetallic alloys, surface modification is achieved by dissolving unstable components, thereby forming a multitude of catalytically active sites. In this study, highly enhanced electrocatalysts are fabricated via chemical etching of mesoporous AuCu alloy nanoparticles prepared through the self‐assembly of micelles. The presence of large mesoporosity (>10 nm) with rich defect sites on the surface, along with the synergistic effect arising from the AuCu bimetallic alloy, effectively boosts electrocatalytic performance for the ethanol oxidation reaction. This strategy demonstrates a promising strategy to further enhance the catalytic performance of Au‐based mesoporous nanoparticles by eliminating the unstable metal component and refining the mesoporous structure with an abundance of various active sites.

Enhancing photocatalytic H2O2 production with Au co-catalysts through electronic structure modification

Gold-based co-catalysts are a promising class of materials with potential applications in photocatalytic H2O2 production. However, current approaches with Au co-catalysts show limited H2O2 production due to intrinsically weak O2 adsorption at the Au site. We report an approach to strengthen O2 adsorption at Au sites, and to improve H2O2 production, through the formation of electron-deficient Auδ+ sites by modifying the electronic structure. In this case, we report the synthesis of TiO2/MoSx-Au, following selective deposition of Au onto a MoSx surface which is then further anchored onto TiO2. We further show that the catalyst achieves a significantly increased H2O2 production rate of 30.44 mmol g−1 h−1 in O2-saturated solution containing ethanol. Density functional theory calculations and X-ray photoelectron spectroscopy analysis reveal that the MoSx mediator induces the formation of electron-deficient Auδ+ sites thereby decreasing the antibonding-orbital occupancy of Au-Oads and subsequently enhancing O2 adsorption. This strategy may be useful for rationally designing the electronic structure of catalyst surfaces to facilitate artificial photosynthesis.

Understanding the mechanism of propane dehydrogenation over coordinatively unsaturated Co-O acid-base pairs and the inhibition effect of trace oxygen

High temperature and a reducing atmosphere are characteristic of propane dehydrogenation (PDH) reaction. Under such condition, the real surface structure of catalysts often differs from that in the ambient environment, particularly for CoOx species with multiple valence states and coordination. Here, a combination of in situ/operando Raman spectroscopy, in situ UV–Vis diffuse reflectance spectroscopy (DRS), and density functional theory (DFT) calculations reveal that coordinatively unsaturated Co-O (Cocu-O) acid-base pairs via lattice oxygen consumption are the PDH active sites of CoOx/Al2O3 catalysts. This highly dispersed Cocu-O species exhibit a C3H6 formation rate and C3H6 selectivity as high as 2 mmol‧gcat−1‧min−1 and 95 %, respectively, which is comparable to most state-of-the-art CoOx-based catalysts. However, industrial C3H8 raw gases typically contain 10–1000 ppm oxygen gas, and the complete eliminating oxygen increases costs. PDH catalytic performance of CoOx/Al2O3 catalysts is sensitive to the extremely low concentration of oxygen gas and is significantly inhibited by it. The fundamental reason is that the concentration of Cocu active sites is determined by the competitive reaction between the filling of trace oxygen on oxygen vacancies and lattice oxygen consumption. The reaction rate of the former is significantly higher than that of the latter. The higher reducibility of CoOx species leads to relatively weaken inhibition of trace oxygen for PDH activity. The oxygen content in the propane feed gas is a non-negligible factor in the development of new Co-based PDH catalysts, especially for their industrial applications.

Modulating the steric effect over high-index facet of MnOx catalysts to enhance toluene oxidation

Engineering surface structures of metal-oxide catalysts are of utmost significance for boosting their catalytic performances. In this work, we reported the high-index (310) facets catalysts (MnOx-AAUS) with oxygen vacancies for VOCs degradation, which was synthesized via an ultrasonic-assisted redox precipitation process. Interestingly, the excellent catalytic performance of MnOx-AAUS catalysts was due to the steric effect between high-index facet with reactants and the simultaneous adsorption-activation of toluene and gaseous oxygen on the high-index (310) facets with oxygen vacancies. The T90% value of the (310) facets catalysts (600 ppm toluene, GHSV = 60,000 mL/g·h, 21 % O2/N2) was significantly lower than that of the previous (001) facets catalysts. Density functional theory (DFT) calculations, along with in-situ FT-IR spectra, revealed that the tilted adsorption configuration of toluene was conducive to simultaneous reaction with the surrounding activated oxygen species. Such the adsorption configuration of toluene/oxygen contributed to the substantially enhanced catalytic activity of the MnOx-AAUS catalyst for VOCs oxidation. This work provides new insights into the roles of high-index facets with oxygen vacancies of MnOx catalysts in the toluene oxidation and paves new avenues for the rational design of highly efficient catalysts for oxidation reactions.

Designing Surface and Interface Structures of Copper-Based Catalysts for Enhanced Electrochemical Reduction of CO2 to Alcohols.

Electrochemical CO2 reduction (ECR) has emerged as a promising solution to address both the greenhouse effect caused by CO2 emissions and the energy shortage resulting from the depletion of nonrenewable fossil fuels. The production of multicarbon (C2+) products via ECR, especially high-energy-density alcohols, is highly desirable for industrial applications. Copper (Cu) is the only metal that produces alcohols with appreciable efficiency and kinetic viability in aqueous solutions. However, poor product selectivity is the main technical problem for applying the ECR technology in alcohol production. Extensive research has resulted in the rational design of electrocatalyst architectures using various strategies. This design significantly affects the adsorption energetics of intermediates and the reaction pathways for alcohol production. In this review, we focus on the design of effective catalysts for ECR to alcohols, discussing fundamental principles, innovative strategies, and mechanism understanding. Furthermore, the challenges and prospects in utilizing Cu-based materials for alcohol production via ECR are discussed.

Regulating Ru−O Bonding Interactions by Ir Doping Boosts the Acid Oxygen Evolution Performance

AbstractHighly active and stable oxygen evolution reaction (OER) catalysts are crucial for the large‐scale application of proton exchange membrane water electrolyzers. However, the dynamic reconfiguration of the catalyst surface structure and active centers is still undefined, which greatly hinders the development and application of efficient OER catalysts. Herein, we report an Ir0.3Ru0.7Ox/C catalyst with a facile low‐temperature synthesis route, which can reach 10 mA cm−2 at an overpotential of 217 mV with a Tafel slope as low as 39.4 mV dec−1, and yields a mass activity 61 times that of commercial IrO2/C at an overpotential of 300 mV. The lattice oxygen structure of RuOx is stabilized by the introduction of Ir species, thus greatly promoting the OER activity and durability. Further in situ Raman reveals that RuOx emerges as the active species at high potentials, and Ru−O bonding interactions are enhanced with Ir regulation, stabilizing the solvation of Ru at high potentials and accelerating the nucleophilic attack of water molecules, leading to the improved OER performance. This work deepens the fundamental understanding of OER and offers an effective way to advance the utilization of Ru‐based OER catalysts.

Le Chatelier’s principle to stabilize intrinsic surface structure of oxygen-evolving catalyst for enabling ultra-high catalytic stability of zinc-air battery and water splitting

Well-designed highly active intrinsic surface structure of a catalyst for oxygen evolution reaction (OER) often faces the problem of corrosion dissolution, which severely deteriorates its catalytic stability, and breaking this activity-stability trade-off has always been a huge and long-term challenge. Herein, we employ Le Chatelier’s principle to address this dissolution problem of the catalyst to maintain its intrinsic surface structure for highly efficient and ultra-stable OER. Taking highly active but susceptible oxygen vacancy-rich Co-W oxide as the model catalyst for alkaline OER, its dissolving kinetics is significantly passivated by introducing homo ions into the electrolyte to regulate the dissolution equilibrium, thus achieving ultralong operating stability without sacrificing its high activity. The theoretical calculations and in-situ experimental results unravel the underlying mechanism of this strategy, that is, the homo ions (tungstate ions) can be preferentially adsorbed on the catalyst surface to construct a local non-corrosive environment, thus effectively stabilizing the well-designed unsaturated active cobalt sites to maintain the intrinsic surface structure of the catalyst and preventing them from being reconstructed or transformed toward the unfavorable direction. Importantly, this strategy is also effective in zinc-air battery and electrolytic water splitting, achieving ultra-stable performance over 1200 h, which is of great importance for promoting the practical applications of low-cost non-noble metal-based catalysts in energy devices.

Construction of CdS@g–C3N4 heterojunction photocatalyst for highly efficient degradation of gaseous toluene

Exploring efficient photocatalysts for the degradation of VOCs under visible light is a challenge. CdS@g–C3N4 heterojunction photocatalytic materials were developed in this study using a microwave-assisted sol-gel process. CdS@g–C3N4(0.2) photocatalyzed the maximum degradation of gaseous toluene under visible light irradiation, and the time required to achieve the same degradation rate was reduced by 270 min when compared to pure CdS. The morphological characterization, photoelectric property analysis, and DFT calculations all verified that the CdS nanoparticles were uniformly disseminated on the surface of g–C3N4, and that the interfaces were closely contacted to form a heterojunction interface with a built-in field. This enhances charge transfer from CdS to g–C3N4 while successfully decreasing electron-hole pair recombination caused by light. Furthermore, the energy band structure was altered to absorb longer wavelengths of light and extend the absorption spectral range, improving the photocatalytic material's efficacy for broad-spectrum light such as sunshine. This paper proposes methods for predicting and optimizing the surface structure of catalysts, as well as developing high-performance multi-heterojunction photocatalysts for the degradation of indoor VOCs.

Co–Fe catalyst supported on acidified bentonite for selective hydrogenation of cinnamaldehyde

Acidified bentonite supported Co and Fe catalyst (Co–Fe/ACBT) with abundant strong Lewis acid sites was used for cinnamaldehyde selective hydrogenation, which showed a great catalytic activity with 90.5% CAL conversion and 86.8% COL selectivity.

Tailoring the facet distribution on copper with chloride.

Electrocatalytic reactions are sensitive to the catalyst surface structure. Therefore, finding methods to determine active surface sites with different geometry is essential to address the structure-electrocatalytic performance relationships. In this work, we propose a simple methodology to tune and quantify the surface structure on copper catalysts. We tailor the distribution and ratio of facets on copper by electrochemically oxidizing and reducing the surface in chloride-rich aqueous solutions. We then address the formation of new facets with voltammetric lead (Pb) underpotential deposition (UPD). We first record the voltammetric lead UPD on different single facets, which have intense peaks at different potential values. We use this data to decouple each facet peak-contribution in the lead (Pb) UPD curves of the tailored and multifaceted copper surfaces and determine the geometry of the active sites. We combine experiments with density functional theory (DFT) calculations to assess the ligand effect of chloride anions on the copper facet distribution during the surface oxidation/electrodeposition treatment. Our experiments and Wulff constructions suggest that chloride preferentially adsorbs on the (310) facet, reducing the number of (111) sites and inducing the growth of (310) or n(100) × (110) domains. Our work provides a tool to correlate active sites with copper geometries, which is needed to assess the structure-performance relationships in electrocatalysis. We also demonstrate an easy method for selectively tailoring the facet distribution of copper, which is essential to design a well-defined nanostructured catalyst.

Ideal Site Geometry for Heterogeneous Catalytic Reactions: A DFT Study

Surface geometry at the atomic level is an important factor related to the activity of a catalytic site. It is important to identify sites with high activity to comprehend the performance of a given catalyst. In this work, it is proposed that the optimal surface for a given reaction step should satisfy the condition ∂E∂xi|TS=0, where E is the transition state energy and xi is any variable characterizing the surface. Taking three elementary steps as examples, it is shown that the optimal site found by this method has significantly reduced TS (transition state) energy compared with facets commonly applied in previous studies, and, thus, it can be several orders more active. The method provides an insight into the geometric impact of catalysis, gives a blueprint for an ideal catalyst surface structure, and, thus, provides guidance for catalyst development.

Operando Surface X-Ray Diffraction Studies of Co Oxide Catalyst Films for Electrochemical Water Splitting

The need for environmental friendly and sustainable energy conversion has triggered renewed interest into the electrochemical and photoelectrochemical splitting of water. A key challenge in this field is the development of economically viable electrocatalyst materials for the oxygen evolution reaction (OER). Transition-metal oxide catalysts, in particular the cobalt (hydr)oxide materials, have been found as promising candidates, since they are earth-abundant, efficient and scalable over a wide range of electrochemical conditions [1]. They present good catalytic properties and stability in alkaline solution under ambient conditions. Although a wide variety of different catalysts with rather diverse nanoscale morphologies have been synthesized and studied, the atomic scale surface structure usually is still unknown or poorly defined. This makes it difficult to compare their electrocatalytic activity and correlate it with ab initio theoretical studies, which hinders the development of clear structure-reactivity relationships and unambiguous determination of the OER reaction mechanism.We presentsystematic comparative studiesof structurally well-defined, 18-35nm thick Co3O4 films, prepared by electrodeposition or physical vapor deposition (PVD) on Au(111), Au(100) and Ir(100) single crystals. In all cases a well ordered epitaxial Co3O4(111) arrangement results, but the film morphology differs substantially, as shown by AFM and surface X-ray diffraction (SXRD). In order to elucidate the quantitative relationship between the catalyst surface structure and the OER reactivity, synchrotron-based operando SXRD and electrochemical measurements were performed simultaneously under reaction conditions, using a dedicated operando cell which allows massive gas evolution and current densities of up to 150 mA/cm2 [2,3].We find that the Co3O4(111) layers prepared by PVD on Ir(100) stay perfectly stable in the pre-OER and OER potential regime, whereas all electrodeposited films exhibit reversible changes in the oxide structure and oxidation state, in agreement with a previous study of Co3O4 catalysts [2]. Specifically, we observe the reverse formation of an ultrathin X-ray-amorphous CoOx(OH)y skin layer above 1 V vs. RHE and the gradual buildup of tensile lattice strain in the underneath, remaining Co3O4 layer with increasing potential. These structural changes occur for all electrodeposited samples, albeit to a different extent, depending on the film morphology [3]. Studying the relationship between the effective thickness of this skin layer and the OER reactivity, we found clear evidence that the entire skin layer is a three dimensional OER zone, which strongly exceeds one monolayer.Our results suggest that even subtle changes of the surface morphology have large influence on the OER activity of the Co3O4 catalyst, which may be expected also for other spinel-type transition metal oxides. On the one hand, this reveals that great care as to be taken in comparing the OER activity of differently prepared catalysts. On the other hand, these observations may provide a base for targeted preparation of highly reactive oxide catalysts.[1] C. C. L. McCrory et al., Journal of the American Chemical Society 2015, 137, 4347.[2] F. Reikowski, et al., ACS Catalysis, 2019, 9, 3811.[3] T. Wiegmann, et al., ACS Catalysis, 2022, 12, 256.

Low temperature reaction mechanism of NH3-SCR reaction on MoOx modified CePO4 catalyst: Combination study on experiments and DFT calculations

Developing CePO4-based NH3-SCR catalysts with high NOx conversion, N2 selectivity, and SO2 tolerance at low temperatures is challenging. Analyzing the atomic-level surface structure of these catalysts is particularly important. Hence, we conducted a combined computational and experimental study to design the surface structure of MoxCe1-xPO4 catalysts, corroborate the reaction performance and structural sensitivity, and investigate the relationship between active sites and structural performance at the atomic level. DFT calculations were used to systematically investigate the NH3 and NO adsorption capacity of the Mo-doped CePO4 solid solution structure model. The rationality of using the Mo-doped CePO4 solid solution structure as a catalyst was further supported by DFT calculation data and experimental results from BET, XRD, Raman, SEM, TEM, HR-TEM, NH3-TPD, H2-TPR, XPS and in situ DRIFTS. The source of the excellent intrinsic NH3-SCR activity of the Mo-doped CePO4 solid solution structure is disclosed. The role of the Mo dopant in the Mo-doped CePO4 solid solution as an SO2 trapping site to protect the catalytic active site from sulfation is discussed from a molecular perspective.

Fabrication of dual-activated coal gangue-loaded nickel-based catalyst for dioctyl phthalate hydrogenation

The development of high-performance and low-cost catalysts is of great significance in the field of catalytic hydrogenation. It is advisable to convert the reserved coal gangue waste into new materials with special functions. Therefore, in this work, dual-activated coal gangue was used as support to prepare Ni-based catalysts that could catalyze the hydrogenation of dioctyl phthalate to synthesize di(2-ethylhexyl) hexahydro-phthalate. The conversion of dioctyl phthalate can reach 99.9 % over the Ni/ZMC-1 catalyst using dual-activated coal gangue as support. This catalyst can be recycled 8 times without obvious loss of its initial activity. Characterization and experimental results revealed that both activation treatments have significant impact on surface structure and composition of catalysts. Thermal activation could remove toxic elements such as S and produce a larger specific surface area, while chemical activation could enhance the dispersion of the active metal and the metal-support interaction, which ultimately improved the activity and stability of the catalyst, simultaneously. This strategy provides a good reference for the high-value utilization of coal gangue and the design of excellent catalyst.

Electrochemical Activity of Carbon-Supported Pt-Nanoparticles: Effect of Pt-Precursor Ligand and/or Presence of Anions During Polyol Synthesis

This study revisits the impacts of the presence of OH− and Cl− anions and/or different forms of Pt precursors during polyol synthesis of carbon-supported electrocatalysts. Efficiency of the synthesis process in terms of the %conversion of a Pt complex to Pt metal has been quantified. It is observed that Pt precursors based on [PtCl6]2− are reduced easily compared to those based on [Pt(OH)6]2−. Furthermore, presence of excess Cl− during synthesis results in decreased %conversion and reduced ECSA, which is opposite from other reported work synthesized at higher temperature and pure solvents. For Pt/C synthesis under mild conditions, 100 °C and 30 vol% EG in water as solvent, presence of OH− during synthesis decreases the ECSA and hence increases the Pt nanoparticle size and change of catalyst surface structure. Finally, a method to get insights into the surface structure of Pt-nanoparticles through analysis of the H-adsorption/H-desorption peaks has been proposed.Graphical

The facilitating effect of sulfide treatment coupled sol-gel method on NH3-SCR activity of Fe–Mn/TiO2 catalysts

The 5Fe–3Mn–S/TiO2-SG catalysts were synthesized by sulfide treatment coupled sol-gel method to develop new NH3-SCR catalysts with wide temperature window, good low-temperature activity and environment-friendly. The evolution of catalyst surface chemical state, morphology, structure, acidity and interaction forces were systematically investigated by XPS, BET, XRD, SEM, H2-TPR, NH3-TPD, UV, IR and steady-state kinetic tests. The influence of sulfide treatment coupled sol-gel method on NO conversion was explored. XRD, BET and SEM characterization revealed that sulfide treatment resulted in smaller catalyst particles and higher dispersion, which increased the specific surface area. XPS, NH3-TPD and steady-state kinetic tests results demonstrated that the sulfide treatment catalysts had a higher surface adsorbed oxygen (Oα) content, which could produce more oxygen vacancies on the catalyst surface, thus increasing the number of acid sites. H2-TPR and UV results demonstrated that the 5Fe–3Mn–S/TiO2-SG catalysts exhibited the strongest contact between the carrier and the active component. The 5Fe–3Mn–S/TiO2-SG catalyst obtained more than 80% NO conversion in the operational temperature range of 220–420 °C, according to the NH3-SCR reaction data. The temperature window was expanded by 120 °C compared to conventional Fe–Mn/TiO2 catalysts, and 98% conversion was achieved at 300 °C. Meanwhile, DFT calculations of the SO42--MnFe2O4(311) crystalline surface of the 5Fe–3Mn–S/TiO2-SG catalysts revealed that it could form stronger chemisorption for both NH3 and NO, which promoted the NH3-SCR reaction more effectively. The DFT calculation results and the experimental findings agreed well.

Promotional effect of Ti on catalytic performance of Cs/Ti-SiO2 for conversion of methyl propionate and formaldehyde to methyl methacrylate

Synthesis of methyl methacrylate (MMA) by aldol condensation of methyl propionate (MP) with formaldehyde (FA) has received researchers’ attention in recent years. Herein, a kind of acid-base bi-functional Cs/Ti-SiO2 was developed for the conversion of MP and FA to MMA. A series of Cs/Ti-SiO2 samples with different acid-base properties were prepared by changing the loading amount of Cs and Ti elements and characterized using XRD, BET, FT-IR, DR UV–vis, SEM, TEM, XPS, CO2/NH3-TPD, O2-TPO, py-IR, and TGA. The introduction of Ti species could significantly regulate the acidity and affect the surface structure of catalyst, facilitating the activation of reactants and aldol reaction effectively. The relationship between the acid-base properties and catalytic activity was correlated, which revealed the crucial role of weak and medium acid sites in this transformative process. The production of MMA was optimized by using response surface methodology (RSM) based on the Box-Behnken design (BBD) approach. As a result, 62.8 % yield of MMA with selectivity of 75.6 % could be achieved at optimal reaction conditions. The catalyst would suffer deactivation from carbon deposition, which could be easily regenerated by simple thermal treatment without any decrease in initial activity during 600 h time-on-stream. Kinetic studies unraveled the activation energy of aldol condensation was 112.2 kJ/mol.