Nanocrystal Catalysts Research Articles

Zinc oxide morphology-dependent CuOx-ZnO interactions and catalysis in CO oxidation and CO2 hydrogenation

CuO/ZnO catalysts with different ZnO morphologies, i.e. nanoplates (p-ZnO) and nanorods (r-ZnO), have been prepared to test for CO oxidation and CO2 hydrogenation. Strong morphology-dependent CuOx-ZnO interactions were observed, which are tightly associated with the ZnO morphology. p-ZnO predominantly exposing polar {002} facets greatly promote the CuOx-ZnO interactions, contributing to the stabilities of CuOx/ZnO catalysts in both reactions. Experimental evidences reveal that CuO-ZnO interfaces act as the active sites in CO oxidation. CuO/p-ZnO catalyst with stronger CuO-ZnO interactions can facilitate the generations of fine CuO and interfacial Cu(I) species, responsible for the adsorption and reactivity of CO and subsequently the high (intrinsic) activity in CO oxidation. However, CuO/ZnO catalysts undergo in situ restructuring to generate Cu/ZnO in CO2 hydrogenation, whose catalytic performance is determined by the key step of CO2 activation. Consequently, Cu/r-ZnO catalyst possessing more surface basic sites exhibits better catalytic performance. These results greatly deepen the fundamental understanding of Cu-based catalysts in both reactions and broaden the concept of morphology-dependent catalysis of oxide-based nanocrystal catalysts that varies with the reactions catalyzed.

Unveiling the Stability of Encapsulated Pt Catalysts Using Nanocrystals and Atomic Layer Deposition.

Platinum exhibits desirable catalytic properties, but it is scarce and expensive. Optimizing its use in key applications such as emission control catalysis is important to reduce our reliance on such a rare element. Supported Pt nanoparticles (NPs) used in emission control systems deactivate over time because of particle growth in sintering processes. In this work, we shed light on the stability against sintering of Pt NPs supported on and encapsulated in Al2O3 using a combination of nanocrystal catalysts and atomic layer deposition (ALD) techniques. We find that small amounts of alumina overlayers created by ALD on preformed Pt NPs can stabilize supported Pt catalysts, significantly reducing deactivation caused by sintering, as previously observed by others. Combining theoretical and experimental insights, we correlate this behavior to the decreased propensity of oxidized Pt species to undergo Ostwald ripening phenomena because of the physical barrier imposed by the alumina overlayers. Furthermore, we find that highly stable catalysts can present an abundance of under-coordinated Pt sites after restructuring of both Pt particles and alumina overlayers at a high temperature (800 °C) in C3H6 oxidation conditions. The enhanced stability significantly improves the Pt utilization efficiency after accelerated aging treatments, with encapsulated Pt catalysts reaching reaction rates more than two times greater than those of a control supported Pt catalyst.

Promoting effects of potassium on ammonia production from electrochemical nitrate reduction over nano-crystal nickel

K+ in the electrolyte promoted the adsorption of NO3− on the nano-crystal nickel catalyst surface and the generation of *H. Consequently, the sluggish NO3− reduction was ameliorated, and elevated performance of NRA was obtained.

Facet-dependent synthesis of H2O2 from H2 and O2 over single Pt atom-modified Pd nanocrystal catalysts

An electron-rich catalyst (Pt1Pd(111)/TiO2) with a prominent facet dependence displays extraordinary catalytic properties in the direct synthesis of H2O2.

Facile and Green Synthesis of Well-Defined Nanocrystal Oxygen Evolution Catalysts by Rational Crystallization Regulation.

The development of catalysts for an economical and efficient oxygen evolution reaction (OER) is critical for clean and sustainable energy storage and conversion. Nickel-iron-based (NiFe) nanostructures are widely investigated as active OER catalysts and especially shape-controlled nanocrystals exhibit optimized surface structure and electronic properties. However, the structural control from amorphous to well-defined crystals is usually time-consuming and requires multiple stages. Here, a universal two-step precipitation-hydrothermal approach is reported to prepare a series of NiFe-based nanocrystals (e.g., hydroxides, sulfides, and molybdates) from amorphous precipitates. Their morphology and evolution of atomic and electronic structure during this process are studied using conclusive microscopy and spectroscopy techniques. The short-term, additive-free, and low-cost method allows for the control of the crystallinity of the materials and facilitates the generation of nanosheets, nanorods, or nano-octahedra with excellent water oxidation activity. The NiFe-based crystalline catalysts exhibit slightly compromised initial activity but more robust long-term stability than their amorphous counterparts during electrochemical operation. This facile, reliable, and universal synthesis method is promising in strategies for fabricating NiFe-based nanostructures as efficient and economically valuable OER electrocatalysts.

Integrated Optimization of Crystal Facets and Nanoscale Spatial Confinement toward the Boosted Catalytic Performance of Pd Nanocrystals.

Tuning the surface chemical property and the local environment of nanocrystals is crucial for realizing a high catalytic performance in various reactions. Herein, we aim to elucidate the structure sensitivity of Pd facets on the surface catalytic hydrogenation reaction and to identify what role the nanoconfinement effect plays in the catalytic properties of Pd nanocrystal catalysts. By controlling the coating structures of mesoporous silica (mSiO2) on Pd nanocrystals with different exposed facets that include {100}, {111}, and {hk0}, we present a series of Pd@mSiO2 nanoreactors in core-shell and yolk-shell structures and the discovery of a partial-coated structure, which can provide different types of nanoconfinement, and we propose a seed size-dominated growth mechanism. We demonstrate that a superior activity was exhibited in Pd nanocrystals enclosed by the {hk0} facet as compared to the Pd{100} and Pd{111} facets, and substantially enhanced efficiency and stability were achieved in Pd@mSiO2 particles with yolk-shell structures, indicating a crucial superiority of optimizing the configuration of crystal facets and nanoconfinement. Our study provides an efficient strategy to rationally design and optimize nanocatalysts for promoting catalytic performance.

Iron phosphide nanocrystals as an air-stable heterogeneous catalyst for liquid-phase nitrile hydrogenation

Iron-based heterogeneous catalysts are ideal metal catalysts owing to their abundance and low-toxicity. However, conventional iron nanoparticle catalysts exhibit extremely low activity in liquid-phase reactions and lack air stability. Previous attempts to encapsulate iron nanoparticles in shell materials toward air stability improvement were offset by the low activity of the iron nanoparticles. To overcome the trade-off between activity and stability in conventional iron nanoparticle catalysts, we developed air-stable iron phosphide nanocrystal catalysts. The iron phosphide nanocrystal exhibits high activity for liquid-phase nitrile hydrogenation, whereas the conventional iron nanoparticles demonstrate no activity. Furthermore, the air stability of the iron phosphide nanocrystal allows facile immobilization on appropriate supports, wherein TiO2 enhances the activity. The resulting TiO2-supported iron phosphide nanocrystal successfully converts various nitriles to primary amines and demonstrates high reusability. The development of air-stable and active iron phosphide nanocrystal catalysts significantly expands the application scope of iron catalysts.

Chiral Perovskite Nanocrystals for Asymmetric Reactions: A Highly Enantioselective Strategy for Photocatalytic Synthesis of N-C Axially Chiral Heterocycles.

Catalytic approaches to generate enantiospecific chiral centers are the major premise of modern organic chemistry. Heterogeneous catalysis is responsible for the vast majority of chemical transformations, yet the direct employment of chiral solid catalysts for asymmetric synthesis is mostly overlooked. Here, we demonstrated that a heterogeneous metal-halide perovskite nanocrystal (NC) catalyst is active for asymmetric organic synthesis under visible-light activation. Chiral 1-phenylethylamine (PEA)-hybridized perovskite PEA/CsPbBr3 NC photocatalysts exhibit an enantioselective (up to 99% enantiomer excess, ee) avenue to produce N-C axially chiral N-heterocycles, i.e., N-arylindoles from N-arylamine photo-oxidation. Mechanistic investigation indicated a discriminated prochiral binding of the N-arylamine substrates onto the chiral-NC surface with ca. -2.4 kcal/mol enantiodifferentiation. Our perovskite NC heterogeneous catalytic system not only demonstrates a promising strategy to address the long-term challenges in atroposelective pharmaceutical scaffold synthesis but also paves the road to directly employ chiral solids for asymmetric synthesis.

Pt Alloy Nanocrystal Catalysts: Diminishing Sizes and Improving Stability

Pt Alloy Nanocrystal Catalysts: Diminishing Sizes and Improving Stability

Harmonious Heterointerfaces Formed on 2D‐Pt Nanodendrites by Facet‐Respective Stepwise Metal Deposition for Enhanced Hydrogen Evolution Reaction

AbstractThe performance of nanocrystal (NC) catalysts could be maximized by introducing rationally designed heterointerfaces formed by the facet‐ and spatio‐specific modification with other materials of desired size and thickness. However, such heterointerfaces are limited in scope and synthetically challenging. Herein, we applied a wet chemistry method to tunably deposit Pd and Ni on the available surfaces of porous 2D−Pt nanodendrites (NDs). Using 2D silica nanoreactors to house the 2D‐PtND, an 0.5‐nm‐thick epitaxial Pd or Ni layer (e‐Pd or e‐Ni) was exclusively formed on the flat {110} surface of 2D−Pt, while a non‐epitaxial Pd or Ni layer (n‐Pd or n‐Ni) was typically deposited at the {111/100} edge in absence of nanoreactor. Notably, these differently located Pd/Pt and Ni/Pt heterointerfaces experienced distinct electronic effect to influence unequally in electrocatalytic synergy for hydrogen evolution reaction (HER). For instance, an enhanced H2 generation on the Pt{110} facet with 2D‐2D interfaced e‐Pd deposition and faster water dissociation on the edge‐located n‐Ni overpowered their facet‐located counterparts in respective HER catalysis. Therefore, a feasible assembling of the valuable heterointerfaces in the optimal 2D n‐Ni/e‐Pd/Pt catalyst overcame the sluggish alkaline HER kinetics, with a catalytic activity 7.9 times higher than that of commercial Pt/C.

Harmonious Heterointerfaces Formed on 2D-Pt Nanodendrites by Facet-Respective Stepwise Metal Deposition for Enhanced Hydrogen Evolution Reaction.

The performance of nanocrystal (NC) catalysts could be maximized by introducing rationally designed heterointerfaces formed by the facet- and spatio-specific modification with other materials of desired size and thickness. However, such heterointerfaces are limited in scope and synthetically challenging. Herein, we applied a wet chemistry method to tunably deposit Pd and Ni on the available surfaces of porous 2D-Pt nanodendrites (NDs). Using 2D silica nanoreactors to house the 2D-PtND, an 0.5-nm-thick epitaxial Pd or Ni layer (e-Pd ore-Ni) was exclusively formed on the flat {110} surface of 2D-Pt, while a non-epitaxial Pd or Ni layer (n-Pd or n-Ni) was typically deposited at the {111/100} edge in absence of nanoreactor. Notably, these differently located Pd/Pt and Ni/Pt heterointerfaces experienced distinct electronic effect to influence unevenly in electrocatalytic synergy for hydrogen evolution reaction (HER). For instance, an enhanced H2 generation on the Pt{110} facet with 2D-2D interfacede-Pddeposition and faster water dissociation on the edge-locatedn-Ni overpowered their facet-located counterparts in respective HER catalysis. Therefore, a feasible assembling of the valuable heterointerfaces in the optimal 2D n-Ni/e-Pd/Pt catalyst overcame the sluggish alkaline HER kinetics, with a catalytic activity 7.9 times higher than that of commercial Pt/C.

Taking the intimidation out of nanocrystal catalyst improvement strategies

Though the many different methods used to enhance nanocatalyst activity may seem overwhelming at first, they can be categorized by how they alter the surface atoms.

Icosahedral Pd Nanocrystal Catalysts with Dispersed Bi Atoms via Photochemical Route for Enhanced Formic Acid Oxidation Reaction

AbstractThe decoration of noble metal catalysts with specific main group or transition metal atoms offers an effective way to improve the catalytic performance through electronic structure regulation and active site optimization without losing the active surface area. Herein, icosahedral Pd nanocrystals catalysts with highly dispersed Bi atoms decoration have been realized by a simple photochemical reduction approach. The decoration of Bi atoms maintains the original Pd cyclic penta‐twinned structure. The deposition amount of Bi atoms, which greatly affect the catalytic performance, is fundamentally regulated by the irradiation time. Compared with pure Pd, the Pd−Bi icosahedral nanocrystals show significant improvement in electrocatalytic activity towards formic acid oxidation. Besides, the catalytic performance is correlated with the content of Bi. The optimal performance is occurred at the Bi content of 2.86%.

Surface engineering of metallic nanocrystals via atomic structure and composition control for boosting electrocatalysis

Since the clean energy industry emerged, developing efficient nanocrystal catalysts has attracted ever-increasing attention. Recently, the utilization of metal nanocrystals as catalysts for electrochemical reactions is entering a new era with the development of theories and techniques that help incorporate surface chemistry into nanoscale materials. Current approaches in the field of nanocrystal catalysts include detailed analyses and modifications of the surface atoms of nanocrystals, with which optimal structures and compositions for target electrochemical reactions could be realized. This review presents two major strategies to engineer the surface structure of nanocrystals: control over the atomic arrangement and composition of nanocrystal surfaces. The first section mainly covers the modification of surface atom arrangements with various methods, including the induction of various facets, strains, and defects. The generation of anomalous crystal structures of nanocrystals is also discussed. The second section encompasses recent advances in controlling the composition of nanocrystal surfaces by bringing high entropy or periodicity to the metal elements in nanocrystals to attain high electrocatalytic activity and stability.

How Size and Strain Effect Synergistically Improve Electrocatalytic Activity: A Systematic Investigation Based on PtCoCu Alloy Nanocrystals.

To reveal how the size effect and strain effect synergistically regulate the mass activity (MA) and specific activity (SA) of Pt alloy nanocrystal catalysts in oxygen reduction reaction (ORR), remains to be difficult due to the highly entangled factors. In this work, six ternary PtCoCu catalysts with sequentially changed composition, size, and compression strain are prepared. It is found that the smaller the alloy particles, the higher the electrochemical active surface area (ECSA) and MA values, that is, the particle size plays a decisive role in the size of the ECSA and MA. While, along alloy size decrease, the intrinsic activity SA first increases, then remains unchanged, and finally rapidly increases again. This detailed analysis shows that for the alloys above 4nm, it is the surface coordination number that decides the SA, while for those below 4nm, it is the well-regulated compression strain that determines the SA. Particularly, Pt47 Co26 Cu27 demonstrates the MA of 1.19 A mgPt -1 and SA of 1.48mA cm-2 , being 7.9 and 6.4 times those of commercial Pt/C respectively, representing an especially superior ORR catalyst.

Uniform Catalytic Nanocrystals: From Model Catalysts to Efficient Catalysts

ConspectusSolid catalysts play a key role in the chemical industry, energy, and the environment. Fundamental understanding of heterogeneous catalysis exerted by solid surfaces is useful for structural designs of efficient catalysts but is challenging due to the complexity. Emerging uniform catalytic nanocrystals (NCs) with controlled and well-defined surface structures have brought new opportunities for fundamental understanding and directed explorations of efficient catalysts. In a previous Account ( Acc. Chem. Res. 2016, 49, 520−527), I postulated and exemplified a concept of oxide nanocrystal model catalysts for the fundamental investigations of oxide catalysis without the “materials gap” and “pressure gap” which are often encountered using the traditional single crystal model catalysts. In this Account, I summarize our effort in fabricating efficient uniform nanocrystal catalysts based on the fundamental understanding of structure–activity relations and reaction mechanisms acquired by oxide nanocrystal model catalyst studies. Directed by the fundamental understanding that the Cu2O{110} facet is active in catalyzing propylene epoxidation with O2 and the fine Cu2O nanocube exposes high densities of Cu2O{110} edge sites, we successfully explore fine Cu2O nanocubes as a highly selective catalyst for propylene epoxidation with O2. Directed by the fundamental understanding that the Cu{100} facet is the active Cu facet in catalyzing the water–gas shift (WGS) reaction, we successfully fabricate a highly active ZnO/fine Cu nanocube WGS catalyst with enhanced ZnO-CuCu{100} active site density. Directed by the fundamental understanding of TiO2 facet effects on the surface band bending and adsorbate–surface interfacial energy level alignment, and consequent photocatalytic performance, we successfully fabricate highly active TiO2{001} NC-based photocatalysts for photocatalytic CH4 conversions. These results adequately exemplify the concept of fundamental understanding-directed explorations of efficient catalysts following a strategy of “identification of active site structure + maximization of active site density”, which, together with the advancement of controlled-synthesis methods, is expected to greatly accelerate the explorations of novel and efficient catalysts in future.

Ag@Pt core-shell icosahedral nanocrystals with solid solution interface improve pH-Universal hydrogen evolution at large current densities

Industrial application of electrochemical hydrogen production urgently requires the development of highly efficient, stable, and inexpensive electrocatalysts that can drive a large current density. Here, Ag@Pt icosahedral nanocrystals (Ag@Pt icosahedral NCs) catalysts were successfully prepared through one-step solvothermal synthesis for addressing those challenges. The synergies of geometric effect and electronic effect triggered by the discrepancy of different components greatly enhance the electrocatalytic performance in the hydrogen evolution reaction (HER) process at large current densities over wide pH ranges. Excitingly, the Ag@Pt icosahedral NCs could reach 4000 mA cm−2 at 232 mV under the acidic medium and also showed efficient catalytic activity in 1 M KOH and 1 M phosphate buffered saline (PBS) media, improving their potential application in industrialization. Density functional theory (DFT) calculation results show that the electronic synergistic effect brought by the core-shell structure weakens the optimal free energy of hydrogen adsorption (ΔGH*), promoting the water decomposition kinetics and greatly achieving high catalytic performance.

High-entropy alloy nanocrystal assembled by nanosheets with d–d electron interaction for hydrogen evolution reaction

Unique PtMoPdRhNi high-entropy alloy nanocrystals (NCs) catalysts assembled by radial nanosheets with multiple active sites with different local chemical environments and the interaction of d–d electron for superior HER performance.

Tailoring Ir-FeOx interactions and catalytic performance in preferential oxidation of CO in H2 via the morphology engineering of anatase TiO2 over Ir-FeOx/TiO2 catalysts

Ir-FeOx/TiO2 catalysts with both Ir and Fe contents of ∼1% wt. employing anatase TiO2 nanocrystals predominantly exposing either {100}, {101}, or {001} facets as the support were prepared and a comprehensive study was conducted on their interactions in pairs that are strongly dependent on the TiO2 morphology. The strongest FeOx-TiO2 interactions occurred over TiO2{001} support while TiO2{101} support contributes to the strongest Ir-TiO2 and Ir-FeOx interactions. Catalytic performance of the Ir-FeOx/TiO2 catalysts in preferential oxidation of CO in H2 is not only affected by the CO reactivity, but also determined by the Ir-FeOx interfaces. Ir-FeOx/TiO2{101} catalyst exhibits the highest CO conversion and best O2 selectivity over the three Ir-FeOx/TiO2 catalysts, which could be ascribed to stronger Ir-FeOx interactions that contribute to the enhancement of a H-spillover effect and subsequently facilitate the transformation of surface carbonaceous intermediates into CO2. These results add the versatility of the morphology engineering strategy in tailoring the structures and catalytic performance of oxide-based catalysts, and broaden the concept of morphology-dependent catalysis of oxide-based nanocrystal catalysts.

Unraveling the Structural Sensitivity of CO2 Electroreduction at Facet-Defined Nanocrystals via Correlative Single-Entity and Macroelectrode Measurements.

The conversion of CO2 into value-added products is a compelling way of storing energy derived from intermittent renewable sources and can bring us closer to a closed-loop anthropogenic carbon cycle. The ability to synthesize nanocrystals of well-defined structure and composition has invigorated catalysis science with the promise of nanocrystals that selectively express the most favorable sites for efficient catalysis. The performance of nanocrystal catalysts for the CO2 reduction reaction (CO2RR) is typically evaluated with nanocrystal ensembles, which returns an averaged system-level response of complex catalyst-modified electrodes with each nanocrystal likely contributing a different (unknown) amount. Measurements at single nanocrystals, taken in the context of statistical analysis of a population, and comparison to macroscale measurements are necessary to untangle the complexity of the ever-present heterogeneity in nanocrystal catalysts, achieve true structure-property correlation, and potentially identify nanocrystals with outlier performance. Here, we employ environment-controlled scanning electrochemical cell microscopy to isolate and investigate the electrocatalytic CO2RR response of individual facet-defined gold nanocrystals. Using correlative microscopy approaches, we conclusively demonstrate that {110}-terminated gold rhombohedra possess superior activity and selectivity for CO2RR compared with {111}-terminated octahedra and high-index {310}-terminated truncated ditetragonal prisms, especially at low overpotentials where electrode kinetics is anticipated to dominate the current response. The methodology framework described here could inform future studies of complex electrocatalytic processes through correlative single-entity and macroscale measurement techniques.