3.1 high entropy effect.
(a) ΔS as a function of the number of principal components for equimolar alloys. (b) Alloy definitions based on configurational entropy. (c) Structural illustration for the FCC, BCC and HCP phases of HEAs. Reproduced from ref. with permission from Frontiers. |
The characteristic of high mixing entropy enhances the mutual solubility among elements and facilitates the formation of simple FCC, BCC or HCP solid solution phases within HEAs during solidification ( Fig. 7c ). 50 Cantor et al. manufactured transition-metal-rich HEAs with six to nine components (the same five elements of Fe, Co, Ni, Cr, and Mn together with other elements such as Cu, Ti, Nb, Ni, Mo, Ta and Ge) in equal atomic ratio, which also forms a single FCC solid solution. 52
In principle, HEAs with a solid solution phase have many merits that can justify them as great potential catalysts. Firstly, they can be produced with wide composition ranges not available in the crystalline form, permitting the fine tuning of their electronic properties to meet catalytic reaction demands. 53 Under the definition of HEAs which consist of more than five elements, we can obtain a total of 7099 possibilities for designing equal-mole HEA systems at an arbitrary choice of a group of 13 metallic elements. 49 Unequal-mole HEAs may also be designed with minor alloying elements like AlCo 0.5 CrCuFe 1.5 Ni 1.2 B 0.1 C 0.15 for further modification of the microstructure and electronic properties. As a result, HEAs offer researchers even more room for design in terms of their composition and electronic properties than traditional alloys. Secondly, the isotropic and homogeneous characters of the alloys allow the active sites in a chemically identical environment. For HEAs, their single-phase character and lack of surface segregation of the alloying elements ensure that the catalytically active species are dispersed uniformly, which would benefit the development of the HEA catalysts with high and exclusive selectivity. 54 Thirdly, the high entropy effect has been considered to be the main reason for the stability of HEAs. The increase of the number of components significantly increases the configurational entropy, and leads to phase stability via a decrease of the Gibbs free energy. 3 It has been reported that the HCP phase of HEA catalysts (IrOsReRhRu) is still retained after heat treatment up to 1500 K and compression to 45 GPa, achieving a record temperature and pressure stability for a single-phase HEA. 55 Due to the large difference in compressibility between Os and other metals, the HEA has higher thermal expansion and lower bulk modulus in comparison with the pure metals in the compositions. 55 In the electrocatalytic oxidation of methanol, the simple-phase character and the high mixing entropy of the elements in HEAs ensure that the active sites are in a uniform dispersion in a homogeneously chemical environment, thus showing pronounced electrocatalytic activity. 55 In the nanostructures of HEA-CoMoFeNiCu, the five principal components are initially randomly assigned to each lattice site, forming a simple FCC phase. Such a solute–solution mixing phase prevents a large miscibility gap which presents in a bimetallic Co–Mo alloy. 56 As shown in Fig. 8 , the randomly mixing surface with uniform distribution of Co and Mo sites optimizes both the dehydrogenation of NH 3 molecules and the desorption of the product N 2 from the HEA surface in the catalytic decomposition reaction of NH 3 . 56
(a) HEA catalysts preventing a large miscibility gap which presents in conventional binary alloys. (b) Schematic illustration of the rate-limiting factors in NH decomposition, labeled with dash lines in the lower panel. On a Co-rich surface (left), the rate is limited by activation or dehydrogenation of NH ; on a Mo-rich surface (right), the rate is limited by the recombinative desorption of *N; the balance for these two steps is reached on an intermediate composition with uniform distribution of Co and Mo atoms. Reproduced from ref. with permission from Springer Nature. |
The multi-metallic cocktail effect can optimize the electronic structures of catalysts. In HEA systems containing Ni and Pd, the electron transfer from Ni to Pd could occur due to the smaller electronegativity of Ni than Pd, which can decrease the Pd–CO binding energy and enhance the catalytic oxidation of methanol molecules. 63 Moreover, the electronic states of metal atoms are altered by alloying with the d-band center of Pd shifting down and the d-band center of Ni shifting up, promoting the electrocatalytic activity of Pd towards methanol/ethanol oxidation and enhancing the adsorption of adsorbates on the Ni sites. 64 The cocktail effect can also alter the charge transfer and chemical ordering of HEAs, as shown in Fig. 9 . In an AlCoCrCuFeNi HEA, the occupied and empty Ni 3d states shift away from the Fermi level, whereas the Cr 3d empty states shift towards the Fermi level, compared to the corresponding pure metals. 65 The charge transfer between the elements in HEAs is negligible due to the compensation of the 3d state occupancy change by the redistribution of delocalized 4s and 4p states of the transition metals. 65 These properties play important roles in the optimization of the adsorption energy of HEAs during catalytic reactions.
The altered properties of HEAs as compared to the corresponding pure metals. A proposed scheme for the DOS redistribution of the Ni and Cr 3d bands occurring upon formation of the AlCoCrCuFeNi HEA. Reproduced from ref. with permission from Elsevier. |
In a word, the cocktail effect in HEAs is generally considered as a complex synergetic mechanism that is responsible for the outstanding catalytic performance of HEAs. The synergistic interactions of the multi-element compositions in HEAs have resulted in a huge divergence of the properties as compared to atoms in single-element metals. But the remarkable thing is that the mechanism of action of such multi-component synergy in HEAs remains largely unknown. The underlying synergistic mechanisms from the view point of lattice distance and electron distribution should be further explored.
The sluggish diffusion effect of HEAs can suppress the degradation caused by the coarsening of nanostructured HEA catalysts. 35,66 Despite the poor corrosion resistance of pure transition metals in strong acid or alkali solution, the high entropy alloy Ni 20 Fe 20 Mo 10 Co 35 Cr 15 composed of such elements showed high corrosion resistance in both acidic and basic electrolytes for the hydrogen evolution reaction (HER). 66 The reasons for the sluggish diffusion effect of HEAs are still controversial. Most of the researchers hold the view that multiple components are responsible for the sluggish diffusion due to low lattice-potential-energy sites provided by small atoms. 35,67 HEAs with multiple principal elements have larger fluctuations in lattice potential energy than pure metals or traditional alloys ( Fig. 10 ). Many low lattice-potential-energy sites always serve as atomic traps and blocks. 67 Thus, if an atom jumps to a low-local-potential state, it would have a low possibility to jump out. In contrast, if an atom jumps to a high-local-potential state, it would have a high chance to hop back to the initial site. Both cases can hinder atomic diffusion and particle coarsening due to the increased energy barrier and activation energy for diffusion. Meanwhile, some other researchers think that certain elements, such as Mn in CoCrFeMnNi alloy, produce a deep potential wall and thus cause a sluggish effect. 67 Therefore, a thorough study should be performed to clarify the origins of the sluggish diffusion effect of HEAs, which in turn helps researchers better design the overall architecture of high-performance HEA catalysts.
Schematic diagram of the variation of low-potential energy and mean difference (MD) during the migration of a Ni atom in different matrices. The MD for pure metals is 0, whereas that for HEA is the largest. Reproduced from ref. with permission from Elsevier. |
The DFT simulation results of (a) the pristine lattice with an ideal FCC structure and (b) the distorted lattice of the CoCrFeNi alloy. Reproduced from ref. with permission from Frontiers. (c) Schematic of the advantages of the lattice-distortion alloys for bifunctional oxygen electrocatalysts. Reproduced from ref. with permission from Elsevier. |
It was reported that the lattice distortion in an Fe-enriched alloy promoted a higher density of active electrons around the Fermi level ( Fig. 11c ). 69 The higher density of activated electrons results in faster electron transfer. In contrast, the electron transfer in alloys with a pristine lattice is quite limited due to the absence of activated electrons. Thus, the alloys with lattice distortion showed improved catalytic performance than alloys with a pristine lattice in catalysis, such as the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). 69 Moreover, some metastable structures (namely fragmented domains such as short-range order, critical defects, amorphous structures, etc. ) may form to accommodate the lattice distortion effect during the preparation of HEAs. 1 Such metastable microstructures are believed to play a key role in enhancing the catalytic performance of HEAs. Lattice distortion can also induce a residual strain field with atomic scale fluctuation, shift the d-band center of catalysts and ultimately affect the catalytic selectivity. The effects of these microstructures and strain on the catalytic performance of HEA catalysts are discussed in detail in Section 3.2 and 3.3, respectively.
In brief, the high-entropy effect simplifies the microstructures of HEAs to form simple solid solution phases, leading to the homogeneous distribution of active site configurations in catalysis. The cocktail effect causes a synthetic effect on properties, wherein the interactions among the different elements may optimize the adsorption energy of the intermediates, thereby enhancing the catalytic activity. The sluggish diffusion effect increases the activation energy and reduces the coarsening kinetics in the grain growth process. It enhances the thermal and chemical stability of HEAs in catalysis. The lattice distortion effect has a great impact on the physical and chemical properties of HEAs, which often results in severe strain due to the atomic size mismatch. Such a strain potentially shifts the d-band center of alloys, and affects the binding modes of intermediates as well as the catalytic selectivity. Moreover, some possible metastable microstructures in the solid-state solution phase of HEAs may form during the preparation process due to the lattice distortion effect, which holds promise for providing a variety of active sites in catalysis.
HEAs | Phase | Synthetic method | Reaction | Mechanisms for improved performance | Ref. |
---|---|---|---|---|---|
PtFeCoNiCuAg | FCC | Sputter | Electrocatalytic methanol oxidation | Not mentioned | |
PtNiCoCuFe | Not mentioned | Electrosynthesis | Electrocatalytic methanol oxidation | Resistance to the poisoning of carbonaceous species | |
IrOsReRhRu | HCP | Pyrolysis | Electrocatalytic methanol oxidation | Not mentioned | |
NiNbPtSnRu | Amorphous | Mechanical milling | Electrocatalytic methanol and CO oxidation | Lower rate of poisoning | |
PtRuCoOsIr | FCC + HCP | Dealloying | Electrocatalytic methanol oxidation and the ORR | The downshift of the Pt d-band weakens the O–O bond | |
AlCoCrTiZn | BCC | Mechanical milling | Catalytic degradation of azo-dyes | Lattice distortion and residual stress lead to a low activation energy barrier | |
AlCrFeMnTi | FCC + BCC | Mechanical milling | Catalytic degradation of azo-dyes | The presence of plenty of nano-galvanic cells among the principal elements | |
AuAgPtPdCu | FCC | Mechanical milling | Electrocatalytic CO reduction | Destabilization of *OCH intermediates and the strong stabilization of *O intermediates | |
NiFeMoCoCr | FCC or FCC + μ | Arc-melting | Electrocatalytic HER | High coordination numbers of single-phase FCC promote the hydrogen adsorption | |
FeCoPdIrPt | FCC | Moving bed pyrolysis | Electrocatalytic HER | The downshift of Pt antibonding states facilitates hydrogen species desorption | |
IrPdPtRhRu | FCC | Polyol method | Electrocatalytic HER | Deeper d-band centre locations (between Ir and Pt) | |
MnFeCoNiCu | FCC | Solvothermal-pyrolysis | Electrocatalytic OER | The presence of lattice defects contributes to the catalytic activity | |
AlNiCoFeX (X = Mo, Nb, Cr) | FCC | Top-down synthesis | Electrocatalytic OER | X atoms prefer high formal oxidation states, facilitating proton migration to O at Ni/Co sites | |
CoFeLaNiPt | Amorphous | Electrosynthesis | Electrocatalytic HER and OER | Synergism between Pt and the other elemental components on the atomic scale | |
PtAuPdRhRu | FCC | Wet chemistry | Electrocatalytic HER and OER | High-entropy at the nanoscale and strong synergistic effects between active metals | |
AlNiCoIrMo | FCC | Dealloying | Electrocatalytic HER and OER | The increased covalency of Ir–O bonds by alloying | |
CrMnFeCoNiNb | Not mentioned | Sputter | Electrocatalytic ORR | Solid solution phase with altered properties overcomes the limitations of the single elements | |
AlCuNiPtMn | FCC | Dealloying | Electrocatalytic ORR | The best electronic modulation for the Pt surface through surface strain and/or ligand effects | |
PtPdFeCoNi | FCC | Carbothermal shock | Electrocatalytic ORR | Rapid electrochemical screening is demonstrated by using a scanning droplet cell | |
Hollow RuIrFeCoNi | FCC | Droplet-to-particle | As the cathode catalyst for Li–O batteries | Maximizing the material usage efficiency by tuning the HEA shell thickness | |
FeCoNiCuMo | FCC | Carbothermal shock | Thermocatalytic NH decomposition | Tunable surface adsorption properties by varying the Co/Mo ratio | |
RuRhCoNiIr | FCC | Carbothermal shock | Thermocatalytic NH decomposition | A synergistic effect from multiple elements, ultrafine size, and homogeneous structure | |
PtPdRhRuCe | FCC | Carbothermal shock | Thermocatalytic NH oxidation | Homogeneous nature of the solid-solution NPs |
Phase transformation during the solidification of an HEA. |
An interesting issue arises regarding the functions of the metastable microstructures in catalytic reactions. Alloys with these microstructures have coordinatively unsaturated sites which are essential for the bonding and activation of the reactants. HEAs have a high concentration of coordinatively unsaturated metal centers (active sites), which makes adsorption 83 and surface reactions 84 easier than on the corresponding crystalline catalysts. Although the effect of such microstructures on the catalytic properties of HEAs has not yet been reported in the literature, their functions in traditional metal/alloy-based catalysts have been demonstrated in detail. 85–87 It has been reported that the presence of unsaturated Ni( II ) binding sites in a nano-porous hybrid material significantly improved hydrogen sorption quantity compared with that of similar materials without unsaturated metals sites. 83 A silver catalyst with stacking faults (defects) and a low coordination number showed superior activity of the hydrogen evolution reaction that outperforms commercial platinum on carbon which is usually considered as the best catalyst. 88 These sites make the adsorption and surface reactions of catalytic intermediates easier than conventional crystalline catalysts, ensuring a high catalytic activity. Catalytic doping of alloys is an effective avenue to improve the hydrogen-storage property of MgH 2 . Compared with crystalline HEAs, amorphous counterparts exhibited better kinetics and lower activation energies during MgH 2 catalysis due to a more uniform distribution of highly refined nanostructures in the amorphous phase. 77 The amorphous alloy catalysts become brittle by absorbing hydrogen, which is beneficial to the formation of refined nanostructures. Consequently, the presence of an amorphous HEA catalyst with the refined nanostructures accelerates hydrogen diffusion in the Mg/MgH 2 matrix, thus enhancing the hydrogen storage properties of MgH 2 . In addition, as the metastable structures are nonporous, the surface reaction would not be affected by diffusion limitations, which is often a problem in traditional heterogeneous catalysis. 89 All these features make HEAs with metastable microstructures attractive in heterogeneous catalysis.
Three substitution effects in alloys: strain, ligand and ensemble effects. |
The mechanical behavior of catalysts is one of the most important factors for the reliable and efficient catalytic reactions, and understanding the role of surface strain in tuning the reaction is critical for catalyst design. 92–97 For instance, as-exfoliated monolayered WS 2 nanosheets exhibited enhanced electrocatalytic activity for hydrogen evolution due to the high concentration of the strained metallic 1T phase. 98 In principle, strain modifies the physical/chemical properties of catalyst surfaces by changing the average energy of the d band. 99 The width of the surface d band was found to be proportional to the interatomic matrix element that describes bonding interactions. The misfit strain changes the width of the d band through changes in the d-orbital interactions between the d orbitals of a metal atom and the d orbitals of its nearest neighbors that are quite sensitive to interatomic spacing. 100 As a consequence of the d width change, the average energy of the d band (the d-band center) moves down or up relative to the Fermi energy in order to maintain a constant d-band filling, resulting in modifications of the strained surface properties. On the basis of the theoretical simulations, the d-band center of catalysts play an important role in their catalytic activity because the d-orbital electrons determine both bond formation and breaking of the intermediate species. 101,102 According to the d-band model, 103 the position of the d-band center determines the adsorption energies and activation energy barriers. The shift of the d-band center influences the bonding and anti-bonding states of adsorbates and reactants on the alloy catalyst surface, and further determines the activity and selectivity of catalytic reactions. 104 To achieve optimal catalytic activity, the d-band center must not be too close or too far from the Fermi level. Notably, the shift trend of the d-band center is reverse for late transition metals (LTMs, for which the d bands are more than half filled) and early transition metals (ETMs) with a less than half-filled d band. Fig. 14 shows the influence of tensile strain on the position of the d band in ETMs and LTMs. 105 ETMs exhibited lower adsorption energies under tensile strain because the expanded lattice reduced the overlap of the wavefunctions and therefore narrowed the metal d band, in contrast to what is observed in LTMs. 105,106 The band narrowing results in an increased population of the d band of LTMs, upshifting the d-band center to preserve the degree of d-band filling. Yan et al. proved that the influence of externally applied elastic strain on the catalytic activity of metal films in the hydrogen evolution reaction (HER) is in a controlled and predictable way. 107 The activities of Ni and Pt were accelerated by compression, while that of Cu was accelerated by tension. 107 Pt-based catalysts exhibited intensive adsorption for catalytic intermediates in the HER and ORR, which was weakened by introducing compressive strain through interface mismatch or size reduction. 108–111 It has been reported that a surface strain of −2.0% would be the best for Pt-based alloy catalysts toward the highest ORR activity. 112,113 DFT has proven that a Pt layer with −2.0% strain would lead to 30 times higher ORR activity than pure Pt. 114 In the experiment, the 3ML-Pt/Pt 25 Ni 75 (111) alloy with −1.7% strain (close to the best strain of −0.2% in theoretical predictions) displayed enhanced activities for the ORR, consistent with the theoretical results. 83 For the FeCoPdIrPt system in the HER, 24 Fe, Co and Pd could downshift the d-band center of Pt, and more electrons could occupy the antibonding states, facilitating the desorption of hydrogen species to produce more hydrogen than the commercial Pt/C catalyst.
The effect of (a and c) tensile and (b and d) compression strain on the position of the d band in early transition metals and late transition metals. |
Considering that catalytic materials are usually nanoscale and the absolute magnitude of the induced strain is very small, strain along a certain direction is defined as ( l f − l i )/ l i , where l i and l f represent the atomic bond length in the initial and final states, respectively. 105 It has been proven that the maximum catalytic activity required an optimum atomic bond length in catalysts. 115 A larger atomic bond length would cause oxygen dissociation before the adsorption in ORRs, whereas a smaller value would generate strong repulsive forces for dual-site adsorption. 115 Furthermore, an optimized surface strain can contribute to a high HER performance due to the small hydrogen adsorption Gibbs free energy on the catalytic sites. 116 Strain-induced changes in the atomic bond length can be viewed as the bulk lattice distortions in catalysts. 105 For HEAs, a serious lattice distortion effect gives rise to changes in the surface strain. The surface strain of HEAs can be tuned by selecting principal components with different atom radii. A seven-component FeNiCoSiCrAlTi HEA coating with BCC solid solution phase was prepared by laser cladding on a low carbon steel substrate. 117 The presence of the small-atomic-radius Si and large-atomic-radius Al and Ti increased the lattice packing density and crystal distortion. The segregation of Ti atom caused the different lattice expansion and growth stress between Ti-depleted polygonal grains and Ti-enriched interdendrites, which can lead to increase of the contraction stress at their interfaces. 117 A higher concentration of Al, which has a larger atomic radius than Co, Ni, Fe, and Cu elements, resulted in a larger lattice distortion of Co 25 Ni 25 Fe 25 A l7.5 Cu 17.5 with transformation of the HEA phase from FCC into a BCC structure. 118–120 This result revealed that the distribution of random elements with various atomic radii in HEAs can induce volume contraction or expansion along the specific direction. In addition, the local lattice distortion can result in the fluctuation of stacking fault (SF) energy. 121,122 The SF energy can change the number of SFs in catalysts, and thus tune their catalytic properties. 16 A high density of SFs in silver NPs caused a low coordination number and high tensile strain, transforming the non-active Ag into a highly active catalyst towards the HER. 116 The different atomic radii of the principal elements in HEAs can induce local strain effects due to the variation of SF energy. 34 SF–SF intersections produced a local strain field, leading to dislocation accumulation and SF formation in order to release the local strain concentration. 34 Based on the above mentioned analysis, it is expected that HEAs can optimize the surface strain, surface d-band width and SF density by selecting principal components with different atomic radii to achieve high catalytic activity. 123
(a) The ligand effect of HEAs and the d-band center shift. The green balls represent noble metal atoms. The orange, purple, blue and yellow balls represent non-noble metal atoms. (b) Changes in the d-band centers for monolayer overlayer on transition metal substrates. Reproduced from ref. with permission from Elsevier. |
Owing to the ligand effect, the reactivity of one metal can be varied substantially by depositing it on another due to the adjustment of the d-band. Fig. 15b displays the d-band center change of a given metal when it is deposited on another metal, calculated by DFT. 125 This helps us to design HEAs with suitable components for a specific catalytic reaction. For instance, Pt is generally used as an anode catalyst for PEM fuel cells. However, the strong binding of CO on the Pt surface leads to poisoning of the catalyst. Finding a catalyst surface that weakly binds CO is desirable. As shown in Fig. 15b , a surface with weaker CO bonds than Pt(111) can be obtained by positioning Pt on top of atoms such as Ir, Rh, Ru, Cu, Fe, and Co, due to the down-shift of the Pt d-band. 125 Likewise, if a surface with stronger adsorption energy of intermediates is required, Pt can be put on atoms such as Ag or Au to up-shift the d-band center.
As lattice strain often changes the electronic structure of alloys, the strain effect and the ligand effect are difficult to be distinguished in practical HEA catalysts. To understand the contribution of the ligand effect, Rossmeisl et al. have isolated the electronic ligand effect of the HEA catalyst (IrPdPtRhRu) from the strain effect by creating an unstrained environment in DFT to investigate its ORR activity ( Fig. 16 ). 126 After statistical analysis of 2000 DFT calculations and subsequent host/guest calculations, it has been found that selected atoms among the fourth nearest neighboring positions in the third layer of an FCC (111) metallic structure have more impact on the bond strength of an adsorbate in the ORR than any second or third nearest atomic positions. 126 It is found that the ligand effect affects both the d-band center and d-band shape which correlates closely with the bond strength of the adsorbate.
Schematic of atomic positions grouped by layer and distance from the binding site on an FCC (111) surface microstructure for (a) on-top adsorption on Pt and (b) fcc hollow site adsorption on IrPdPt. The fourth layer contains zones 4A, 4B, 4C and 4D and has an identical layout to the first layer. (c) Overview of the regression coefficients of the least squares fits for each element by zone. The atoms with direct coordination (i.e., zones 1A and 2A) to the binding atoms have a large effect on the binding energy of the intermediate. Zone 3B has a similar sized impact on the binding energy to the neighbors in zone 2A. Reproduced from ref. with permission from John Wiley and Sons. |
Alloys with distinct atomic ensembles result in different absorber binding strengths. When Au alloys with Pt as the catalyst in allyl alcohol hydrogenation, the H atoms are only adsorbed onto Pt sites. 127 Au atoms, which simply act as a surface diluent, have no impact on the H binding energy. PtAu catalysts exhibit a linear increase in activity with increasing Pt ratios. 127 However, when Pt atoms are replaced by Pd, H can interact with both Pd and Au atoms. Thus, the binding energy strength of H atoms on the Pd–Au atomic surface ensemble can be tuned to achieve improved hydrogenation activity. The contrasting behavior of PtAu and PdAu alloys is because different effects work in these two systems. The ensemble effect dominates the PtAu system, whereas PdAu alloys exhibit both ensemble and ligand effects. The ligand effect results in the direct charge transfer from Au to Pd atoms, leading to the d-band perturbation. These results provide valuable guidance for tuning the absorber binding energy by screening suitable components in HEAs.
Overall, the strain, ligand, ensemble effects and the d-band perturbation can significantly affect the adsorption energy of intermediates in catalytic reactions. The following section mainly discusses the relationship between the adsorption energy and catalytic activity of HEA catalysts.
(a) Scheme of active site distribution within one adsorption peak. (b) Visualized intrinsic current response in the kinetic region of these grouped active sites, considering their activity as well as the intensity. (c) Scheme of correlations between a complex solid solution (CSS) NP structure, its effect on the adsorption energy distribution pattern, and the respective electrochemical response in the kinetic region. Reproduced from ref. with permission from John Wiley and Sons. |
The optimization of adsorption energy has also been found when a nanocrystalline AuAgPtPdCu HEA was used for the electrocatalytic reduction of CO 2 . 9 The faradaic efficiency is near 100% with respect to gaseous products at −0.3 V vs. reversible hydrogen electrode (RHE) due to a large number of catalytic sites present randomly on the surface of the HEA NPs, highlighting the uniqueness of the HEAs. 9 In CO 2 reduction, the conversion of *OCH 3 into the *O intermediate, which is an endoergic reaction, has been considered the rate-determining step due to the high barrier. DFT calculation, based on the free-energy calculations of intermediates, demonstrated that the barrier is much lower for the HEA system (1.35 eV) than for the pristine Cu(111) (1.95 eV), as shown in Fig. 18 . 9 The fact that the CO 2 reduction on the HEA NPs over the Cu(111) is thermodynamically favored should be attributed to the easier destabilization of *OCH 3 intermediates and the stronger stabilization of *O intermediates on the HEA surface than the Cu(111) surface. For stabilization of *O, both Pd 11 and Cu 7 atoms can bond O atoms on the HEA NP surface. 9 Notably, despite the presence of five elements in the HEA catalyst, the electrocatalytic activity is predominantly described by Cu atoms, and other atoms only provide a synergetic effect. 9
(a) Schematic of the electrocatalytic reduction of CO on the surface of a AuAgPtPdCu HEA. (b) X-ray diffraction (XRD), (c) transmission electron microscopy (TEM) bright-field image, and (d) high-resolution scanning transmission electron microscopy (HR-STEM) image of AuAgPtPdCu HEAs; the inset of (c) shows a high magnification image of a single AuAgPtPdCu HEA nanoparticle. (e) Chemical homogeneity of Au, Ag, Pt, Pd, and Cu. (f) Optimized structure of the special quasi-random structure of the AuAgPtPdCu HEA. (g) Free-energy diagram of CO reduction reaction on the AuAgPtPdCu surface. The inset shows the optimized structures of the intermediates on the HEA surface. Gray, green, pink, yellow, blue, brown, red, and orange spheres represent Pt, Pd, Ag, Au, Cu, C, O, and H atoms, respectively. Reproduced from ref. with permission from the American Chemical Society. |
Electrochemical HER is a classic two-electron-transfer reaction occurring through the Volmer–Heyrovsky mechanism. This mechanism involves two steps: Volmer step (H + + e − + * → H*) and Heyrovsky step (H + + e − + H* → 0.5H 2 + *). The corresponding free energy changes of the two steps are given by Δ G Volmer = E H ads + Δ E ZPE − T Δ S H and Δ G Heyrovsky = − E H ads − (Δ E ZPE − T Δ S H ), where E H ads is the hydrogen adsorption energy, Δ E ZPE and Δ S H are the difference in zero-point energy and the entropy difference between the adsorbed state and H 2 , respectively. 133 Thus, E H ads determines the overall HER activity. It has been found that the catalytic activity shows a volcano trend as a function of the hydrogen adsorption strength on catalyst sites ( Fig. 19a ). 134 The activity can be optimized when the adsorption energy of hydrogen species on catalysts is close to 0 V due to the balance of adsorption and desorption. 97 Although Pt is a high-activity catalyst for the HER, its scarcity limits its application. HEAs are expected to decrease the loading of noble metals without losing their electrocatalytic efficiencies as the cocktail effect can optimize the adsorption strength of hydrogen. In the FeCoPdIrPt system, the combination of Co with strong adsorption and Ir with weak adsorption can moderate the free energy of H species. 24 Pd, despite its poor HER activity, can modulate the hydrogen binding energy on the Pt surface. 97 Thus, the synergic effect of the atoms in the HEA NPs leads to excellent activity towards the HER. 24 In another work, an amorphous HEA of CoFeLaNiPt has also been found to show improved electrocatalytic performance compared to the individual components during the HER due to the elemental synergisms between Pt and other components on the atomic scale ( Fig. 19b ). 6
(a) Current density as a function of hydrogen adsorption energy. Reproduced from ref. with permission from the American Chemical Society. (b) Electrocatalytic O and H evaluation of a CoFeLaNiPt HEMG-NP (High-Entropy Metallic Glasses-nanoparticle) electrocatalyst. Each material was loaded onto the HOPG (highly oriented pyrolytic graphite) substrate. Reproduced from ref. with permission from Springer Nature. |
The ORR in fuel cells usually involves four-proton–electron transfer to form H 2 O. 135 During this process, the adsorption energy of intermediates such as O, OH and OOH on the surface of catalysts determines the catalytic activity of the ORR. The activity of metals with strong adsorption of the intermediates is limited by the proton transfer to the intermediates. For metals with weak adsorption of the intermediates, oxygen is unstable on the catalyst surface, thus no transfer of protons and electrons to oxygen occurs. A theoretical volcano-like trend between the activity and intermediate adsorption energy is also observed ( Fig. 20a and b ). Although Pt is near the top of the volcano-like trend, there still exists an overpotential of ca. 0.4 V for the ORR. 136,137 Pt-based alloys can reduce the overpotential by optimizing the intermediates' adsorption energy related to the pure Pt catalyst. 138,139 A first principles study has proven that transition metals can weaken the adsorption of chemical species to the Pt, leading to higher ORR activity. 140 Fig. 20c compares the calculated free energies of the steps in the ORR on CuNiPt and CuNiPtMn HEA surface systems. 79 The generation of the OOH* intermediate is the rate-limiting step of the ORR on both catalyst surfaces. Compared with CuNiPt, the addition of Mn in CuNiPtMn modulates the electronic properties of the catalyst surface, and thus optimizes the binding of OOH through the cocktail effect, resulting in enhanced activity ( Fig. 20d and e ). 79 The cocktail effect has also been found to be applicable to design advanced ORR catalysts without Pt, such as AlCuNiAgMn, AlCuNiAgMo, and AlCuNiAgCo, which even outperform the pure Pt catalyst. 79 The fact that the cocktail effect can optimize the adsorption energy of intermediates in the ORR is also proven by density functional theory (DFT), as shown in Fig. 21 . 141 In order to achieve a highly efficient ORR reaction, *OH and *O intermediates must not be too stable on the surface of catalysts nor be easily removed. While Pt(111) is the best crystal surface of pure metal for the ORR, the adsorption energy of *OH (∼0.1 eV) on it is still too strong. 136 According to the DFT results, the surface of an HEA catalyst can offer a near-continuous distribution of adsorption energy due to the complicated surface configurations. 141 Thus, a high-efficiency ORR can be achieved by tuning the compositions of the HEA catalyst with optimal adsorption energy close to the peak of the Sabatier volcano curve. 142 The HEA materials become a design platform for new alloys by increasing sites with superior catalytic activity to pure Pt(111).
Trends in ORR activity as a function of (a) the O adsorption energy or (b) both the O and the OH binding energy. Reproduced from ref. with permission from the American Chemical Society. (c) Free energy profiles of the ORR steps on the PtCuNiMn and PtCuNi. Adsorption configurations of the OOH on the (d) PtCuNi and (e) PtCuNiMn models. The colors dark blue, pink, brown, green, red and white represent the atoms of Pt, Mn, Cu, Ni, O and H, respectively. Reproduced from ref. with permission from Elsevier. |
(a) *OH on-top binding. Orange (1): binding site. Light green (2): surface neighbors are coordinating once to the binding site. Light gray (3): subsurface neighbors are coordinating once to the binding site. (b) *O FCC hollow site binding. Dark green (4): surface neighbors are coordinating twice to the binding site. Dark gray (5): subsurface neighbors coordinating twice to the binding site. Distribution of adsorption energies for (c) Ir Pd Pt Rh Ru , (d) Ir Pd Pt Rh Ru , (e) Pd Ru , and (f) Ir Pt (global maximum activity). A represents the activity. Reproduced from ref. with permission from Elsevier. |
Firstly, scientific theories for the construction of HEAs is scarce. There are a huge number of possible compositions and combinations of properties in the HEA field. Wise element design strategies for suitable compositions and structures to fit the requirements in heterogeneous catalysis thus become especially important. The rational design of HEA nanomaterials from fundamental principles has the potential to create catalysts with high activity and selectivity. 147 Until now, designing new HEA materials is based on the traditional trial-and-error method which becomes very difficult due to the large number of possible compositions for HEAs. As the combinations of composition and process for producing HEAs are numerous, each HEA has its own microstructure and properties to be identified and understood. It is very important to present basic concepts relating to HEAs in advance. Using principles of materials science is the most basic way to design a new material. This route can be used at the beginning to develop new HEA nanomaterials for desired properties by fully understanding the properties of components in materials, such as the crystal structure, atomic size, atomic weight, redox potential, electronegativity, melting and boiling points, density, electron configuration, etc. Rapid-throughput screening approaches are required to vet potential HEA compositions. For example, if we want to design low-density HEAs, more light elements should be used. If HEAs with oxidation resistance are needed, more oxidation-resistant elements such as Al, Cr, and Si should be selected. If HEAs with BCC phases are desired, Al can be added by strong binding with other elements to promote the formation of a BCC phase. In catalysis, Pd instead of Pt can be chosen as one of the components in HEAs to promote the catalytic activity due to the high electro-oxidation catalytic activity and lower price of Pd. In addition, both leverage neural network (NN) and machine learning can be employed to provide insights for rational design of HEA catalysts. The NN strategy can account for the three substitution effects of HEAs (mentioned in Fig. 13 ) for predicting the adsorption energy of catalysts. 148 Machine learning can help calculate adsorption energies of all surface sites on catalysts, allowing the optimization of the HEA compositions. 9,76 Nevertheless, there is also a risk that promising alloys might be dismissed in the early stage by these methods, due to the absence of exploration of the complex links between microstructures and properties. Certainly, careful experimental assessment of HEAs is the prerequisite to obtain the microstructure characteristics and stability.
Secondly, moderate and scalable synthesis strategies are urgently needed. Although current methods mentioned in Chapter 4 have successfully crafted HEA NPs, they generally require rigorous conditions such as high pressure, temperature and inert atmospheric protection. NPs can be only immobilized on limited thermally resistant substrates rather than thermally sensitive ones. It may incur great stoichiometric deviation due to the high vapor pressure of metal elements under these extreme conditions. The mild electrosynthesis method can only craft amorphous NPs (electrosynthesis method 6 ) or is limited by the corresponding targets (PLA approach 44 ). It is urgent to develop a more convenient technology with low energy consumption under mild conditions for synthesizing a library of HEA nanostructures.
Thirdly, although HEAs have shown great potential in catalysis applications, the understanding of the whole HEA world and how HEA materials behave in complex catalysis environments is still at the infant stage. Several future trends are pointed out: more fundamental studies on HEA structures are required . In most cases, the catalytic performance of HEA catalysts is simply explained by the synergetic effect between multiple elements. Very limited studies aim to establish an in-depth understanding of the structure–performance relationship. HEA structures with mutual interactions between different atoms, lattice distortion, metastable structures, stacking fault energy, electrical and thermal conductivity, diffusion coefficients, corrosion and oxidation are desired to fully understand the relationship between the structure and performance. Moreover, a theoretical model including microstructure details in HEAs will be instructive for establishing an accurate structure–performance relationship over HEA catalysts. Architectures in the atomic structures of HEAs can be explored in a systematic and site-specific manner. Otherwise, the possibility of comprehensively exploring such systems would be precluded. Accurate models for catalyst selections need to be built . The lack of such models makes the design of high-activity HEA catalysts difficult. The chosen descriptors determined the catalytic activities of catalysts. For example, the Sabatier principle shows a volcano-type relationship between catalytic activities and adsorption energy, whereas it is a linear relationship in the Brønsted–Evans–Polanyi behavior. 149,150 Due to the interactions of elements in alloys, the properties in terms of adsorption energy may be more complex. Establishing a descriptor suitable for HEA materials will contribute to guiding the selection of high-activity catalysts. The behavior of HEA NPs in real service environments is investigated . In the application of industrial catalysis, critical environments, such as high temperature/pressure, oxidizing/reducing conditions, and extreme pH solution, are usually involved. 151 Since it is challenging to obtain structural and compositional information of such nanoscale HEAs at spatial and temporal resolution, there is still very limited knowledge of the behavior of HEA NPs in these environments. Shahbazian-Yassar et al. employed in situ gas-cell TEM to investigate the oxidation behavior of Fe 0.28 Co 0.21 Ni 0.20 Cu 0.08 Pt 0.23 HEA NPs at 400 °C and in an atmospheric pressure air environment ( Fig. 22 ). 152 Although the overall oxidation kinetics of the HEA NPs are slower than that of both monometallic and bimetallic alloy NPs with similar principal elements, the oxidation of HEA NPs governed by the Kirkendall effect has been found involving outward diffusion of Fe, Co, Ni, and Cu to form an oxide layer with a concentration gradient. Pt stays in the HEA core region during the oxidation process due to its nonreactivity. Studies on other extreme conditions such as oxidizing/reducing conditions and extreme pH solution are also needed, yet are still scarce, but are crucial for understanding HEA behavior in these environments and providing insights in designing chemical/thermal corrosion-resistant alloys for various applications.
(a) Schematic of the in situ gas-cell in air. (b) In situ TEM image sequences of HEA NPs during annealing in air to study the oxidation of HEA NPs. (c) Exemplary atomic model for an oxidized slab after equilibration. (d) Schematic illustration of the oxidation process of HEA NPs. Reproduced from ref. with permission from the American Chemical Society. |
Fourthly, more research can be focused on high-entropy ceramics (HECs) such as nitrides, carbides, oxides, and sulfides. A few studies have indicated that four core effects of HEAs are also applicable in HECs. As some conventional phosphides/sulfides/oxides/carbides/nitrides have been proven as efficient catalysts, 153–157 HECs are expected to have promising applications in catalysis via their four core effects. Unfortunately, there are few reports on the synthesis of HEC nanomaterials, limiting their research in the field of catalysis.
Based on these deliberations, HEAs have thrust us into a new world of seemingly infinite possibility. Research on HEA-based catalysis has been attracting increasing attention. Recent studies indeed offer significant potential to improve our fundamental understanding of the catalytic behavior of HEAs. Nevertheless, future efforts should focus on key features presented by the microstructures of HEAs, rather than wandering in its limitless expanse.
Acknowledgements.
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The new film Nickel Boys , opening the New York Film Festival on September 27 after a debut in Telluride, is an adaptation of Colson Whitehead ’s Pultizer-winning novel, a fictionalized account of a real Florida-panhandle reform school whose staff, for decades, abused and in some cases murdered its charges—particularly the Black boys sent there ostensibly for rehabilitation. It is sorrowful, damning subject matter, of the sort that might merit sprawling cinematic treatment.
But director RaMell Ross , a photographer turned documentarian now making his scripted feature debut, takes an entirely different tack in approaching this hefty material. His film is shot mostly in first-person perspective; as an unlucky teenager, Elwood ( Ethan Herisse ), finds himself dragged into this swampy hell, we watch what unfolds through his eyes. Peripheral vision is limited. Ross tunnels into the heart of a helpless tragedy in narrow framing; we understand the forces bearing down on Elwood, but we rarely see them in full.
Nickel Boys is the most formally inventive of its fall-movie-season brethren, a bold swing of a literary adaptation that mostly earns its gimmick. Though really, gimmick is a cheap word for what Ross is doing. The nervy technical conceit of Nickel Boys has an instructive purpose; it is not mere “look what I can do” grandstanding. Ross has designed his film as a plunge into the visceral realities of racism in America, with no outside framing offering even a hint of escape.
It’s a tough film, rigorous in its intent. But Ross does allow for grace, comfort, quotidian beauty. The opening stretches of his film show us Elwood’s pre-incarceration life in all its precarious potential: he’s a promising student, doted on by the grandmother who raised him ( Aunjanue Ellis-Taylor ), in puppy-dog love with a girlfriend, grasping in happy amazement at a future rushing toward him. It’s the mid-1960s in Florida and Elwood is a young Black man, so he is certainly faced with daunting obstacles. But he has, out of both passion and principled intellect, decided to stand on the front lines of the struggle he shares with so many. This is an engaged, determined kid, a portrait crafted in flickering mosaic.
Even if Elwood were on a less noble track, though, that would in no way justify the harsh punishment he receives when he unwittingly hitches a ride in a stolen car, is picked up by the police, and is remanded to Nickel Academy. Ross is careful to insist that no child, of any background, deserves such routine dehumanization. But yes: we are meant to particularly mourn for the future stolen from Elwood, who followed all the rules and was nonetheless relegated to brutal subjugation. Nickel Boys is a stark reflection of our country’s gruesome record; even after emancipation, Black men routinely found themselves dragged into a kind of slavery different only in name.
Ross has made a busy collage of a film, jumping between evocative image and plot with a swiftness that sometimes leaves the audience on the outside. We are not really left to sit in any one particular experience—either of joy or confinement—long enough for it to fully seep in. Ross’s stuttering poetry is more considered than simply stylish, but is not quite as emotionally enveloping as more traditional narrative might be.
Ross does not hew strictly to his central device. The film breaks away from Elwood’s gaze on occasion to show us that of his fellow prisoner Turner (the remarkable Brandon Wilson ), a more rebellious free-spirit than his quiet and cowed friend. Stitched together, Elwood and Turner’s perspectives create an intimate picture of ragged and wary optimism. Deliverance must be possible, and yet it cannot be assumed.
The details of Elwood and Turner’s hardship are sometimes directly confronted. More often than not, though, they are only alluded to. Ross insightfully, shrewdly renders how such a nightmare might be processed, especially by someone so young and naive as Elwood. The danger is close by, but life also must plug along. It is only in hindsight, maybe, that the scope of what happened—to Elwood, to everyone—can truly be grasped. Ross makes room for that recollection, drifting into the future (shooting from behind actor Daveed Diggs ’s head) to show what adulthood looks like for men struggling to reclaim the humanity robbed of them as teenagers.
Nickel Boys closes in walloping fashion: a final series of sensory flashes serves as heartbreaking coda. One wonders how much more might be felt had Ross laid things out more linearly, had he taken the time to truly delve into particular moments, to flesh out the dimensions of Elwood and Turner’s daily life.
Still, Ross’s elegant, thorough re-creation of time and place is plenty effective as is. And anyway, is witnessing explicit trauma really any more valuable than what Ross chooses to show us? Nickel Boys is perhaps a rebuke to the idea that violence must be plainly stated in order to be understood. Here, it is palpably present in every negative space. What Ross instead affords these young men is the dignity of a point of view, drawing the viewer into the bracing immediacy of mind and body. Nickel Boys is an arduous—and also humane and lovely—trek in another’s shoes. It’s an immersion into two lives that evokes the histories of countless more.
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COMMENTS
Isaac Newton Eyes Optics. Experimental result: The nature of color and light. When: 1665-1666. Before he was that Isaac Newton — scientist extraordinaire and inventor of the laws of motion, calculus and universal gravitation (plus a crimefighter to boot) — plain ol' Isaac found himself with time to kill.
Pavlov's Dog: And 49 Other Experiments That Revolutionised Psychology by Adam Hart-Davies, Elwin Street, 2018. A very quick run through of a few more famous scientific experiments. Opening Skinner's Box: Great Psychological Experiments of the 20th Century by Lauren Slater, Bloomsbury, 2005/2016.
3. Bobo Doll Experiment Study Conducted by: Dr. Alburt Bandura. Study Conducted between 1961-1963 at Stanford University . Experiment Details: During the early 1960s a great debate began regarding the ways in which genetics, environmental factors, and social learning shaped a child's development. This debate still lingers and is commonly referred to as the Nature vs. Nurture Debate.
3: Henry Cavendish weighs the world (1798) In Cambridge, England, one of the world's greatest physics laboratories is named for Henry Cavendish, an 18th-century scientist who weighed the world. Quite an undertaking, you might think! Actually, Cavendish's famous experiment involved measuring the density of Earth, from which its mass (or weight ...
2. Freeze Water Instantly. When purified water is cooled to just below freezing point, a quick nudge or an icecube placed in it is all it takes for the water to instantly freeze. You can finally ...
10 Cool Chemistry Experiments. ThoughtCo / Hilary Allison. Chemistry is king when it comes to making science cool. There are many interesting and fun projects to try, but these 10 chemistry experiments might be the coolest. Whether you want to witness color transformations with copper and nitric acid or create a foam spectacle with hydrogen ...
Musical Jars Science Experiment. This super easy experiment is simple as it is fun! Kids make their own musical instruments with clear jars and water then investigate sound waves, pitch, and more. When the experiment is complete, use the colorful new "instrument" for a fun music lesson. Kids can play and take turns to "name that tune"!
Go Science Kids. 43. "Flip" a drawing with water. Light refraction causes some really cool effects, and there are multiple easy science experiments you can do with it. This one uses refraction to "flip" a drawing; you can also try the famous "disappearing penny" trick.
10 Scientific Discoveries That Changed The World. DNA, gravity, and germ theory are a few of the key findings in history that forever shifted the course of human civilization. Learn how these scientific discoveries changed the world. By Allison Futterman and Monica Cull. Jan 18, 2024 7:30 AMJan 18, 2024 8:27 AM.
What Makes Ice Melt Fastest? Build a Paper Roller Coaster. Elephant Toothpaste. Make Popping Boba Balls Out of Your Drinks. Make the Wind Work for You! Tallest Paper Tower Challenge. How to Turn a Potato Into a Battery. Bath Bomb Science. Make Ice Cream in a Bag.
They have made great strides in lifting that veil of mystery. In addition to providing us with food for stimulating party conversations, some of the most famous psychological experiments of the last century reveal surprising and universal truths about nature. ... 10. Rosenbaum's experiment. Among the most interesting investigations in this ...
Here are the top 10 greatest physics experiments of all time that have shed light on some of the mysteries that surround us. 1. Galileo Galilei's Experiment on Speed of Falling Objects. Before Galileo, Aristotle had argued that heavy objects fall at a faster rate than lighter objects. But Galileo who is famed for his work on gravity, motion ...
10 Great Experiments That Contribute to Modern Psychology 1. Milgram's Experiment: In the Milgram experiment, a subject's willingness to administer a certain amount of shock served as a proxy for obedience. Even though several of the subjects became quite anxious, upset, and hostile toward the researcher, they nevertheless obeyed ...
With that in mind, here are our top 20 picks for the BEST science experiments to do at home with your kids! Baking Soda and Vinegar Experiments. There are so many cool experiments you can do with these pantry staples. Yes, you can do a standard volcano, but you can also hatch dino eggs, create fireworks, set off explosive bottle rockets and more!
Simple Science Experiments with Baking Soda and Vinegar. Baking soda + vinegar = a great chemical reaction! This fizzy reaction can fuel a variety of simple science experiments at home. First of all, we have tested and found out the absolute best combination of baking soda and vinegar to get the best reaction possible.
#10: Blood Model in a Jar. Teaches Kids About: Human biology; Difficulty Level: Easy; Messiness Level: Medium; This blood model experiment is a great way to get kids to visual what their blood looks like and how complicated it really is. Each ingredient represents a different component of blood (plasma, platelets, red blood cells, etc.), so you ...
Thermite Reaction. The thermite reaction is one of the more dramatic chemistry experiments. All you do is mix a metal and a metal oxide and ignite it. But, this is no ordinary fire. The reaction is very bright and extremely hot. It is the burning of metal, so it serves as an example of oxidation, combustion, and exothermic reactions.
These experiments make great family projects to do together, too - much better than vegetating in front of the TV! Below you will find a selection of science experiments spanning biology, chemistry, physics and Earth sciences. Each section will list the equipment you need, some instructions, and an explanation of what happens. ...
Here's a list of over 30 Science Fair ideas to get you started. Then download science experiments, and watch experiment videos to inspire your project.
The human family tree expanded significantly in the past decade, with fossils of new hominin species discovered in Africa and the Philippines. The decade began with the discovery and ...
Wash and dry your hands. Leave the eggs in the glasses for 12 hours. After 12 hours, remove the eggs from the glasses of soda one at a time. Rinse them in cool water and pat them dry with the ...
AS SEEN ON THE ELLEN DEGENERES SHOW! · 50 fantastic experiments from bestselling author Steve Spangler · All experiments vetted by the scientists at the Smithsonian Institution · Step-by-step instructions with full color photos Smithsonian 10-Minute Science Experiments gives curious young readers dozens of colorful, exciting projects designed to teach them about the basics of science ...
Science experiments you can do at home! Explore an ever growing list of hundreds of fun and easy science experiments. Have fun trying these experiments at home or use them for science fair project ideas. Explore experiments by category, newest experiments, most popular experiments, easy at home experiments, or simply scroll down this page for tons of awesome experiment ideas!
Lu et al. developed a fast-moving bed pyrolysis (FEBP) strategy to synthesize HEA NPs on granular supports including carbon, γ-Al 2 O 3 and zeolite ().This method was conducted at 923 K with a population speed of 20 cm s −1, resulting in the formation of a small size (∼2 nm) of HEA NPs within 5 s.The critical size of HEA nucleus is small enough to reduce excess free energy used for ...
42mm: 46mm: Dimensions: 42 x 36 x 9.7 mm: 46 x 39 x 9.7 mm: IP rating: IP6X: IP6X: Display resolution: 446 x 374 pixels: 496 x 416 pixels: Display size: 1.77 inches: 1.96 inches
"This is the greatest office in the world." Go inside the epic return of Yellowstone. New episodes drop Nov. 10 at 8/7c, only on Paramount Network. #Yellowst...
The new film Nickel Boys, opening the New York Film Festival on September 27 after a debut in Telluride, is an adaptation of Colson Whitehead's Pultizer-winning novel, a fictionalized account of ...