Self-Optimized Ligand Effect of Single-Atom Modifier in Ternary Pt-Based Alloy for Efficient Hydrogen Oxidation.

Modifying the atomic and electronic structure of platinum-based alloy to enhance its activity and anti-CO poisoning ability is a vital issue in hydrogen oxidation reaction (HOR). However, the role of foreign modifier metal and the underlying ligand effect is not fully understood. Here, we propose that the ligand effect of single-atom Cu can dynamically modulate the d-band center of Pt-based alloy for boosting HOR performance. By in situ X-ray absorption spectroscopy, our research has identified that the potential-driven structural rearrangement into high-coordination Cu-Pt/Pd intensifies the ligand effect in Pt-Cu-Pd, leading to enhanced HOR performance. Thereby, modulating the d-band structure leads to near-optimal hydrogen/hydroxyl binding energies and reduced CO adsorption energies for promoting the HOR kinetics and the CO-tolerant capability. Accordingly, PtPdCu1/C exhibits excellent CO tolerance even at 1,000 ppm impurity.

Remote Synergy between Heterogeneous Single Atoms and Clusters for Enhanced Oxygen Evolution.

Integrating single atoms and clusters into one system is a novel strategy to achieve desired catalytic performances. Compared with homogeneous single-atom cluster catalysts, heterogeneous ones combine the merits of different species and therefore show greater potential. However, it is still challenging to construct single-atom cluster systems of heterogeneous species, and the underlying mechanism for activity improvement remains unclear. In this work, we developed a heterogeneous single-atom cluster catalyst (ConIr1/N-C) for efficient oxygen evolution. The Ir single atoms worked in synergy with the Co clusters at a distance of about 8 Å, which optimized the configuration of the key intermediates. Consequently, the oxygen evolution activity was significantly improved on ConIr1/N-C relative to the Co cluster catalyst (Con/N-C), exhibiting an overpotential lower by 107 mV than that of Con/N-C at 10 mA cm-2 and a turnover frequency 50.9 times as much as that of Con/N-C at an overpotential of 300 mV.

Neighbouring Synergy in High-Density Single Ir Atoms on CoGaOOH for Efficient Alkaline Electrocatalytic Oxygen Evolution.

The catalytic performance of single-atom catalysts was strictly limited by isolated single-atom sites. Fabricating high-density single atoms to realize the synergetic interaction in neighbouring single atoms could optimize the adsorption behaviors of reaction intermediates, which exhibited great potential to break performance limitations and deepen mechanistic understanding of electrocatalysis. However, the catalytic behavior governed by neighbouring single atoms is particularly elusive and has yet to be understood. Herein, we revealed that the synergetic interaction in neighbouring single atoms contributes to superior performance for oxygen evolution relative to isolated Ir single atoms. Neighbouring single atoms was achieved by fabricating high-density single atoms to narrow the distance between single atoms. Electrochemical measurements demonstrated that the Nei-Ir1/CoGaOOH with neighbouring Ir single atoms exhibited a low overpotential of 170 mV at a current density of 10 mA cm-2, and long-durable stability over 2000 h for oxygen evolution. Mechanistic studies revealed that neighbouring single atoms synergetic stabilized the *OOH intermediates via extra hydrogen bonding interactions, thus significantly reducing the reaction energy barriers, as compared to isolated Ir single atoms. The discovery of the synergetic interaction in neighbouring single atoms could offer guidance for the development of efficient electrocatalysts, thus accelerating the world's transition to sustainable energy.

Torsion Angles between Donor and Acceptor Moieties as a Descriptor for Designing Nonlinear Optics and Thermally Activated Delayed Fluorescence Materials.

The performances of nonlinear optics (NLO) and thermally activated delayed fluorescence (TADF) materials are strongly related to the torsion angles (θ) between donor (D) and acceptor (A) moieties in D-A architecture molecules. However, the underlying relationships connecting θ to the performances of NLO/TADF materials remain unclear. Herein, we present a comprehensive theoretical study on NLO/TADF materials composed of a series of D-A backbone molecules (TPAAP/TPAAQ series and AQ-DMAC/AQ-MeFAC series) to shed light on these relationships. It is found that changing θ via the intramolecular locking strategy can greatly influence values of the first hyperpolarizability (ß) and singlet-triplet energy gap (ΔEST), further leading to better/worse performances of NLO/TADF materials, respectively. Intriguingly, a more detailed analysis indicates that the variation trends between θ and ß/ΔEST are changeable in low θ regions, exhibiting volcano-like relationships. The large coefficients of determination (R2, ranging from 0.76 to 0.93) suggest that this experimentally measurable parameter (θ) can be used as a promising descriptor to evaluate the performances of related materials. Following the revealed θ-ß/θ-ΔEST correlations, the optimal/worst torsion angles for different materials are identified. These findings highlight the importance of the intrinsic structure-performance relationships, thus providing novel design strategies for high-performance NLO/TADF materials.

Electronic Spin Moment As a Catalytic Descriptor for Fe Single-Atom Catalysts Supported on C2N.

The electrocatalytic activity of transition-metal-based compounds is strongly related to the spin states. However, the underlying relationship connecting spin to catalytic activity remains unclear. Herein, we carried out density functional theory calculations on oxygen reduction reaction (ORR) catalyzed by Fe single-atom supported on C2N (C2N-Fe) to shed light on this relationship. It is found that the change of electronic spin moments of Fe and O2 due to molecular-catalyst adsorption scales with the amount of electron transfer from Fe to O2, which promotes the catalytic activity of C2N-Fe for driving ORR. The nearly linear relationship between the catalytic activity and spin moment variation suggests electronic spin moment as a promising catalytic descriptor for Fe single-atom based catalysts. Following the revealed relationship, the ORR barrier on C2N-Fe was tuned to be as low as 0.10 eV through judicious manipulation of spin states. These findings thus provide important insights into the relationship between catalytic activity and spin, leading to new strategies for designing transition metal single-atom catalysts.

CO oxidation on Ru-Pt bimetallic nanoclusters supported on TiO2(101): The effect of charge polarization.

Pt-based catalyst is widely used in CO oxidation, while its catalytic activity is often undermined because of the CO poisoning effect. Here, using density functional theory, we propose the use of a Ru-Pt bimetallic cluster supported on TiO2 for CO oxidation, to achieve both high activity and low CO poisoning effect. Excellent catalytic activity is obtained in a Ru1Pt7/TiO2(101) system, which is ascribed to strong electric fields induced by charge polarization between one Ru atom and its neighboring Pt atoms. Because of its lower electronegativity, the Ru atom donates electrons to neighboring Pt. This induces strong electric fields around the top-layered Ru, substantially promoting the adsorption of O2/CO + O2 and eliminating the CO poisoning effect. In addition, the charge polarization also drives the d-band center of the Ru1Pt7 cluster to up-shift to the Fermi level. For surface O2 activation/CO oxidation, the strong electric field and d-band center close to the Fermi level can promote the adsorption of O2 and CO as well as reduce the reaction barrier of the rate-determining step. Meanwhile, since O2 easily dissociates on Ru1Pt7/TiO2(101) resulting in unwanted oxidation of Ru and Pt, a CO-rich condition is necessary to protect the catalyst at high temperature.

The O, OH and OOH-assisted selective coupling of methanol on Au-Ag(111).

Using density functional theory (DFT) calculations, we performed a thorough theoretical investigation on the catalytic mechanism of oxidative self-coupling of methanol with molecular oxygen on Au-Ag catalysts. It is found that molecular oxygen can be activated via a hydroperoxyl (OOH) intermediate by taking a hydrogen atom from co-adsorbed methanol with an energy barrier of 0.51 eV, which is actually the rate determining step for the overall reaction. The O, OH and OOH oxidant formation proceeds via two channels of I and II with low barriers. We demonstrated that the oxidative coupling of methanol by OOH, atomic oxygen, and hydroxyl is much more favorable than the total oxidation of methanol, and is responsible for the high selectivity of Au-Ag catalysts in methanol oxidation. The revealed activation mechanism provides an efficient pathway for optimizing the selective coupling of methanol with dioxygen.

A theoretical study of O2 activation by the Au7-cluster on Mg(OH)2: roles of surface hydroxyls and hydroxyl defects.

Using density functional theory (DFT) calculations, we investigated O2 activation by the Au7-cluster supported on the perfect and hydroxyl defective Mg(OH)2(0001) surface. It is revealed that hydroxyl groups on the perfect Mg(OH)2(0001) surface can not only enhance the stability of the Au7-cluster, but also help the adsorption of the O2 molecule through hydrogen-bonding interactions with the 2nd-layered interfacial Au sites. Density of states (DOS) analysis shows that the d-band centers of the 2nd-layered interfacial Au atoms are very close to the Fermi level, which thereby reduce the Pauli repulsion and promote the O2 adsorption. These two responses make the 2nd-layered interfacial Au atoms favor O2 activation. Interestingly, the surface hydrogen atoms activated by the 1st-layered Au atoms can facilitate the O2 dissociation process as well. Such a process is dynamically favorable and more inclined to occur at low temperatures compared to the direct dissociation process. Meanwhile, the hydroxyl defects of Mg(OH)2(0001) located right under the Au7-cluster can also up-shift the d-band centers of the surrounding Au atoms toward the Fermi level, enhancing its catalytic activity for O2 dissociation. In contrast, the d-band center of Au atoms surrounding the hydroxyl defect near the Au7-cluster exhibits an effective down-shift to lower energies, and therefore holds low activity. These results unveiled the roles of surface hydroxyls and hydroxyl defects on the Au/Mg(OH)2 catalyst in O2 activation and could provide a theoretical guidance for chemists to efficiently synthesize Au/hydroxide catalysts.

The roles of surface structure, oxygen defects, and hydration in the adsorption of CO(2) on low-index ZnGa(2)O(4) surfaces: a first-principles investigation.

The effects of the surface atomic and electronic structures, oxygen defects, and hydration on CO2 adsorption on ZnGa2O4(100), (110), and (111) surfaces were studied using density functional theory (DFT) slab calculations. For the perfect (100) surface, the most stable adsorption state involved the Zn-O-Ga bridge site, with an adsorption energy of 0.16 eV. In the case of the (110) and (111) surfaces, the strongest binding occurred on the Zn-O bridge sites, with much lower adsorption energies of -0.22 eV and -0.35 eV, respectively. In addition, the perfect surfaces showed CO2 activation ability, but dissociation adsorption could not proceed. The oxygen vacancies on these three surfaces (1) made the metal sites beside them carry less positive charge and further reduced the adsorption energies on these metal sites, and (2) created efficient adsorption sites that allowed even dissociative adsorption. The most favorable molecular and dissociative adsorption states both involved the O3c vacancy site of the (100) surface, and these two processes were spontaneous with adsorption energies of 0.74 eV and 0.80 eV, respectively. When H2O molecules are present on the perfect and defective surfaces, the generation of hydrogen bonds between H2O and CO2 would slightly enhance the stability of adsorption (except for that on the surface), making them energetically favorable. However, the co-adsorption of H2O could also increase the energy barriers for the decomposition reactions on the defective surfaces, making them kinetically unfavorable. Furthermore, the oxygen vacancy defects showed good activity for H2O adsorption and decomposition, as well. Thus, when both H2O and CO2 were present in the adsorption system, H2O would compete with CO2 for the oxygen vacancy sites and further decrease the amount of CO2 adsorption and decomposition. These findings have important implications for the decomposition of CO2 on the ZnGa2O4 surfaces and can provide theoretical guidance for chemists to efficiently synthesize ZnGa2O4 catalysts.

Distance effect of single atoms on stability of cobalt oxide catalysts for acidic oxygen evolution.

Developing efficient and economical electrocatalysts for acidic oxygen evolution reaction (OER) is essential for proton exchange membrane water electrolyzers (PEMWE). Cobalt oxides are considered promising non-precious OER catalysts due to their high activities. However, the severe dissolution of Co atoms in acid media leads to the collapse of crystal structure, which impedes their application in PEMWE. Here, we report that introducing acid-resistant Ir single atoms into the lattice of spinel cobalt oxides can significantly suppress the Co dissolution and keep them highly stable during the acidic OER process. Combining theoretical and experimental studies, we reveal that the stabilizing effect induced by Ir heteroatoms exhibits a strong dependence on the distance of adjacent Ir single atoms, where the OER stability of cobalt oxides continuously improves with decreasing the distance. When the distance reduces to about 0.6 nm, the spinel cobalt oxides present no obvious degradation over a 60-h stability test for acidic OER, suggesting potential for practical applications.

A theoretical study of water adsorption and decomposition on low-index spinel ZnGa2O4 surfaces: correlation between surface structure and photocatalytic properties.

Water adsorption and decomposition on stoichiometrically perfect and oxygen vacancy containing ZnGa2O4 (100), (110), and (111) surfaces were investigated through periodic density functional theory (DFT) calculations. The results demonstrated that water adsorption and decomposition are surface-structure-sensitive processes. On a stoichiometrically perfect surface, the most stable molecular adsorption that could take place involved the generation of hydrogen bonds. For dissociative adsorption, the adsorption energy of the (111) surface was more than 4 times the energies of the other two surfaces, indicating it to be the best surface for water decomposition. A detailed comparison of these three surfaces showed that the primary reason for this observation was the special electronic state of the (111) surface. When water dissociated on the (111) surface, the special Ga3c-4s and 4p hybridization states at the Fermi level had an obvious downshift to the lower energies. This large energy gain greatly promoted the dissociation of water. Because the generation of O(3c) vacancy defects on the (100) and (110) surfaces could increase the stability of the dissociative adsorption states with few changes to the energy barrier, this type of defect would make the decomposition of water molecules more favorable. However, for the (111) surface, the generation of vacancy defects could decrease the stability of the dissociative adsorption states and significantly increase their energy barriers. Therefore, the decomposition of water molecules on the oxygen vacancy defective (111) surface would be less favorable than the perfect (111) surface. These findings on the decomposition of H2O on the ZnGa2O4 surfaces can be used toward the synthesis of water-splitting catalysts.

Design of Efficient Oxygen Reduction Reaction Catalysts with Single Transition Metal Atom on N-Doped Graphdiyne.

The revelation of the underlying structure-property relationship of single-atom catalysts (SACs) is a fundamental issue in the oxygen reduction reaction (ORR). Here we present systematic theoretical and experimental investigations of various N-doped graphdiyne (NGDY) supported transition metals (TMs) to shed light on this relationship. Calculation results indicate that the TMs' comprehensive activities follow the order of Pd@NGDY > Ni@NGDY > Co@NGDY > Fe@NGDY, which fits well with our experimental conclusion. Moreover, detailed structure-property relationship (194 in total) analysis suggests that the key-species binding stability (ΔG*OH), the d-orbital center (εd/εd-a) and charge transfer (ΔQTM/ΔQTM-a) of the active metal before/after reactants adsorption and the bond length of TM-O (LTM-O) as descriptors can well reflect the intermediate binding stability or ORR activity on different TM-SACs. Specifically, the change trend of catalytic activity is opposite to that of intermediate binding stability, meaning that too strongly bonded *OOH, *O, and *OH intermediates are unfavorable for ORR.

Catalytic Descriptor Exploration for Ru-Based Fischer-Tropsch Catalysts: Effect of Chlorine and Sulfur Addition.

As an important factor in the design of catalysts, catalytic descriptor exploration has emerged as a novel frontier in heterogeneous catalysis. Here, the underlying structure-activity relationships of Ru-based catalysts are theoretically studied to shed light on this area. Calculations of different competing reaction paths suggest that the HCO*-mediated path─because of two synergistic active sites─is more favorable than others. In addition, compared to unadulterated Ru catalysts, the presence of Cl enhances the hydrocarbon production, whereas the presence of S decreases it. After a systematic examination of a series of structure-activity relationships (42 in total), we found that both charge transfer and average charge difference of active Ru atoms are good descriptors for the binding stability of reactants. However, for reactivity the Gibbs free energy of the reactants performs better. More interestingly, due to the quite different catalytic processes of the dissociation and hydrogenation steps, their correlations have opposite slopes.

Carbon Monoxide Oxidation Promoted by Surface Polarization Charges in a CuO/Ag Hybrid Catalyst.

Composite structures have been widely utilized to improve material performance. Here we report a semiconductor-metal hybrid structure (CuO/Ag) for CO oxidation that possesses very promising activity. Our first-principles calculations demonstrate that the significant improvement in this system's catalytic performance mainly comes from the polarized charge injection that results from the Schottky barrier formed at the CuO/Ag interface due to the work function differential there. Moreover, we propose a synergistic mechanism underlying the recovery process of this catalyst, which could significantly promote the recovery of oxygen vacancy created via the M-vK mechanism. These findings provide a new strategy for designing high performance heterogeneous catalysts.

Catalytic Chemistry Predicted by a Charge Polarization Descriptor: Synergistic O2 Activation and CO Oxidation by Au-Cu Bimetallic Clusters on TiO2(101).

The versatile properties of bimetallic nanoparticles greatly expand the range of catalyzed chemical reactions. We demonstrate that surface chemistry can be understood and predicted using a simple adsorbate-surface interaction descriptor that relates charge polarization to chemical reactivity. Our density functional theory studies of O2 activation and CO oxidation catalyzed by Au7-Cu1 bimetallic nanoparticles supported on the TiO2(101) surface demonstrate that the generated oxidized Cu atom (CuO x) can efficiently inhibit the aggregation of the active Cu sites. Moreover, because of the strong dipole-dipole interaction between the surface and the adsorbate on the oxidized Cu site, the adsorption of CO + O2/CO + O can be significantly enhanced, which can decrease the CO oxidation barriers and further improve catalytic performance. The product of the two electric dipole moments provides a parameter that allows us to predict the key catalytic properties for different adsorption sites and reaction pathways. The reported findings provide important insights into the mechanism of chemical reactivity of metallic clusters and generate a valuable principle for catalyst design.

Enhanced Activity of C2N-Supported Single Co Atom Catalyst by Single Atom Promoter.

The remarkable chemical activity of metal single-atom catalysts (SACs) lies in their unique electronic states associated with the low-coordination nature of single-atom sites. Yet, electronic state manipulation normally requires direct contact with other atoms, which inevitably changes the low-coordination environment. Herein, we found by first-principle calculations that the activity of a Co SAC for HCOOH dehydrogenation is appreciably enhanced via electronic state manipulation by a noncontact single atom promoter. A Co atom and a Sn/Ge/Pb atom are anchored in the same cavity of a graphitic C2N monolayer. Surprisingly, the nonbonded promoter makes two far splitting spin states of Co almost degenerate via charge redistribution of C2N support. Further, the high-spin Co gives a remarkably low reaction barrier comparable to Pt or Pd catalysts. Our results demonstrate that the activity of a SAC can be tuned via a noncontact promoter, casting new insights into electronic state modulation of SACs on graphene-like support.

Defect Effects on TiO2 Nanosheets: Stabilizing Single Atomic Site Au and Promoting Catalytic Properties.

Isolated single atomic site catalysts have attracted great interest due to their remarkable catalytic properties. Because of their high surface energy, single atoms are highly mobile and tend to form aggregate during synthetic and catalytic processes. Therefore, it is a significant challenge to fabricate isolated single atomic site catalysts with good stability. Herein, a gentle method to stabilize single atomic site metal by constructing defects on the surface of supports is presented. As a proof of concept, single atomic site Au supported on defective TiO2 nanosheets is prepared and it is discovered that (1) the surface defects on TiO2 nanosheets can effectively stabilize Au single atomic sites through forming the Ti-Au-Ti structure; and (2) the Ti-Au-Ti structure can also promote the catalytic properties through reducing the energy barrier and relieving the competitive adsorption on isolated Au atomic sites. It is believed that this work paves a way to design stable and active single atomic site catalysts on oxide supports.

A First-Principle Study of Synergized O2 Activation and CO Oxidation by Ag Nanoparticles on TiO2(101) Support.

We performed density functional theory (DFT) calculations to investigate the synergized O2 activation and CO oxidation by Ag8 cluster on TiO2(101) support. The excellent catalytic activity of the interfacial Ag atoms in O2 dissociation is ascribed to the positive polarized charges, upshift of Ag d-band center, and assistance of surface Ti5c atoms. CO oxidation then takes place via a two-step mechanism coupled with O2 dissociation: (i) CO + O2 → CO2 + O and (ii) CO + O → CO2. The synergistic effect of CO and O2 activations reduces the oxidation energy barrier (Ea) of reaction (i), especially for the up-layered Ag atoms not in contact with support. It is found that the coadsorbed CO and O2 on the up-layered Ag atoms form a metal-stable four-center O-O-CO structure motif substantially promoting CO oxidation. On the oxygen defective Ag8/TiO2(101) surface, because of the decreased positive charges and the down-shift of d-band centers in Ag, the metal cluster exhibits low O2 adsorption and activation abilities. Although the dissociation of O2 is facilitated by the TiO2(101) defect sites, the dissociated O atoms would cover the defects so strongly that further CO oxidation would be prohibited unless much extra energy is introduced to recreate oxygen defects.

Theoretical study of H2O adsorption on Zn2GeO4 surfaces: effects of surface state and structure-activity relationships.

We employed the density functional theory to investigate the interaction of H2O with Zn2GeO4 surfaces, considering both perfect and defective surfaces. The results revealed that the interaction of H2O with Zn2GeO4 surfaces was dependent on the structure of the latter. For perfect surfaces, H2O adsorbed at the Ge3c···O2c site of a (010) surface could spontaneously dissociate into an H atom and an OH group, whereas H2O tended to adsorb at the O2c-M3c-O3c site of a (001) surface by molecular adsorption. The presence of oxygen defects was found to strongly promote H2O dissociation on the (010) surface. Analysis of the surface electronic structure showed a large density of Ge states at the top of the valence band for both perfect and defective (010) surfaces, which is an important factor affecting H2O dissociation. In contrast, perfect and defective (001) surfaces with surface Ge states buried inside the valence band were significantly less reactive, and H2O was adsorbed on these surfaces in the molecular form. This information about the adsorbate geometries, catalytic activity of various surface sites, specific electronic structure of surface Ge atoms, and their relevance to surface structure will be useful for the future design of the Zn2GeO4 photocatalyst, as well as for the atomistic-level understanding of other structure-sensitive reactions.