Transition Metal Single-atom Catalysts Research Articles

Interfacial adsorption and catalysis of single-atom Pt-loaded ZrO2 surfaces for enhancing formaldehyde oxidation

The emerging transition metal single-atom catalysts (SACs) are expected to have high activity for converting detrimental formaldehyde (HCHO) under mild conditions. Currently, the exploitation of novel SACs with designed or modified support surfaces remains largely imperative. Herein, we used density functional theory to explore the catalytic performance for HCHO oxidation on various single-atom Pt-loaded ZrO2 surfaces, in which oxygen vacancy and lattice hydroxyl group were included on the surfaces. The surface modifications could enhance the co-adsorption of HCHO and O2 molecules and provide more active sites due to interfacial electron redistribution. The transition state search approach was applied to investigate the oxidation pathways on various ZrO2-supported SAC surfaces, wherein distinct dehydrogenation mechanisms and intermediates were clarified. The oxygen vacancy defects and hydroxyl groups can enhance the catalytic activity for HCHO oxidation by providing active receptor sites for the H-transfer and facilitating the CH bond breakage. Microkinetic modeling was further used to characterize the reaction rates and kinetics behavior of HCHO oxidation on the SAC surfaces. Our simulation demonstrates the excellent catalytic performance of the modified ZrO2-supported SAC in the HCHO oxidation. Meanwhile, the mechanism is also an important implication for the synthesis and design of novel SACs.

Regulating coordination environment around transition metal (Fe, Co) single atom catalysts for efficient Hg0 adsorption

Elemental mercury (Hg0) is one of the main pollutants released during coal combustion, which is difficult to remove due to its hydrophobicity and volatility, resulting in serious environmental pollution. Therefore, it is urgent to develop a low-cost and high-performance catalyst to remove Hg0. In this work, using first-principles study, the effect of nonmetal (NM = B, C and O) coordination environment on the charge distribution of graphene-supported transition metal single atom catalysts (TM-N4-SAC) has been investigated. It is found that regulating the TM-N4-SAC with NM coordination atoms with fewer valence electrons than N atom can cause TM atoms to lose more electrons, and the charge distribution in the active center to be locally deviated. Moreover, in-depth analysis of the adsorption configuration, charge density difference, charge transfer, adsorption energy and density of state of Hg0 adsorption on NM modified TM-N4-SAC confirmed that the adsorption of Hg0 can be effectively enhanced only when TM atoms lose more electrons. Thus, Fe-N3B- and Co-N3B-SAC have the strongest ability to adsorb Hg0 because they have the most negative adsorption energy of −1.13 and −0.49 eV. This work provides theoretical guidance for the design of SAC for efficient adsorption of Hg0.

Atomic-Level Asymmetric Tuning of the Co1-N3P1 Catalyst for Highly Efficient N-Alkylation of Amines with Alcohols.

Despite the extensive development of non-noble metals for the N-alkylation of amines with alcohols, the exploitation of catalysts with high selectivity, activity, and stability still faces challenges. The controllable modification of single-atom sites through asymmetric coordination with a second heteroatom offers new opportunities for enhancing the intrinsic activity of transition metal single-atom catalysts. Here, we prepared the asymmetric N/P hybrid coordination of single-atom Co1-N3P1 by absorbing the Co-P complex on ZIF-8 using a concise impregnation-pyrolysis process. The catalyst exhibits ultrahigh activity and selectivity in the N-alkylation of aniline and benzyl alcohol, achieving a turnover number (TON) value of 3480 and a turnover frequency (TOF) value of 174-h. The TON value is 1 order of magnitude higher than the reported catalysts and even 37-fold higher than that of the homogeneous catalyst CoCl2(PPh3)2. Furthermore, the catalyst maintains its high activity and selectivity even after 6 cycles of usage. Controlling experiments and isotope labeling experiments confirm that in the asymmetric Co1-N3P1 system, the N-alkylation of aniline with benzyl alcohol proceeds via a transfer hydrogenation mechanism involving the monohydride route. Theoretical calculations prove that the superior activity of asymmetric Co1-N3P1 is attributed to the higher d-band energy level of Co sites, which leads to a more stable four-membered ring transition state and a lower reaction energy barrier compared to symmetrical Co1-N4.

Modulation of Photocatalytic CO2 Reduction by n-p Codoping Engineering of Single-Atom Catalysts.

Transition metal (TM) single-atom catalysts (SACs) have been widely applied in photocatalytic CO2 reduction. In this work, n-p codoping engineering is introduced to account for the modulation of photocatalytic CO2 reduction on a two-dimensional (2D) bismuth-oxyhalide-based cathode by using first-principles calculation. n-p codoping is established via the Coulomb interactions between the negatively charged TM SACs and the positively charged Cl vacancy (VCl) in the dopant-defect pairs. Based on the formation energy of charged defects, neutral dopant-defect pairs for the Fe, Co, and Ni SACs (PTM0) and the -1e charge state of the Cu SAC-based pair (PCu-1) are stable. The electrostatic attraction of the n-p codoping strengthens the stability and solubility of TM SACs by neutralizing the oppositely charged VCl defect and TM dopant. The n-p codoping stabilizes the electron accumulation around the TM SACs. Accumulated electrons modify the d-orbital alignment and shift the d-band center toward the Fermi level, enhancing the reducing capacity of TM SACs based on the d-band theory. Besides the electrostatic attraction of the n-p codoping, the PCu-1 also accumulates additional electrons surrounding Cu SACs and forms a half-occupied dx2-y2 state, which further upshifts the d-band center and improves photocatalytic CO2 reduction. The metastability of Cl multivacancies limits the concentration of the n-p pairs with Cl multivacancies (PTM@nCl (n > 1)). Positively charged centers around the PTM@nCl (n > 1) hinders the CO2 reduction by shielding the charge transfer to the CO2 molecule.

Sp/sp2 carbon ratio-driven high-throughput screening of electrocatalytic nitrogen reduction performance on transition metal single-atom catalysts

Sp/sp2 carbon ratio-driven high-throughput screening of electrocatalytic nitrogen reduction performance on transition metal single-atom catalysts

Main Group SnN4O Single Sites with Optimized Charge Distribution for Boosting the Oxygen Reduction Reaction.

Transition metal single-atom catalysts (SACs) have been regarded as possible alternatives to platinum-based materials due to their satisfactory performance of the oxygen reduction reaction (ORR). By contrast, main-group metal elements are rarely studied due to their unfavorable surface and electronic states. Herein, a main-group Sn-based SAC with penta-coordinated and asymmetric first-shell ligands is reported as an efficient and robust ORR catalyst. The introduction of the vertical oxygen atom breaks the symmetric charge balance, modulating the binding strength to oxygen intermediates and decreasing the energy barrier for the ORR process. As expected, the prepared Sn SAC exhibits outstanding ORR activity with a high half-wave potential of 0.912 V (vs RHE) and an excellent mass activity of 13.1 A mgSn-1 at 0.850 V (vs RHE), which surpasses that of commercial Pt/C and most reported transition-metal-based SACs. Additionally, the reported Sn SAC shows excellent ORR stability due to the strong interaction between Sn sites and the carbon support with oxygen atom as the bridge. The excellent ORR performance of Sn SAC was also proven by both liquid- and solid-state zinc-air battery (ZAB) measurements, indicating its great potential in practical applications.

Fully exposed copper single-atom sites on mesoporous N/S-codoped graphene for efficient zinc-air battery

Transition metal single-atom catalysts are recently emerging as the most potential candidates for the oxygen reduction reaction due to their remarkable activity and durability, yet subjected to limited availability proportion of active sites to reactant in practice due to the lack of favorable morphology. Herein, the ultrathin mesoporous N/S-codoped graphene is fabricated by a potassium thiocyanate (KSCN) assisted pyrolysis of metal-organic framework (ZIF-8) as the robust substrate for anchoring copper single-atom sites. The KSCN-assisted pyrolysis can not only create N and S coordination atoms but also regulate the fully exposed morphology. The graphene-supported copper single-atom catalysts (g-Cu-SACs) show typical mesoporous structure with larger surface area of 1612 m2 g–1. Spectral and microscopy results reveal highly isolated Cu single-atom sites on mesoporous graphene with unsymmetrical Cu-S1N3 structure. Theoretical analysis demonstrated that the asymmetric coordination environment effectively enhanced O2 adsorption and facilitated the ORR performance. The g-Cu-SACs show excellent catalytic activity in alkaline oxygen reduction reaction with a half-wave potential of 0.920 VRHE and good cycling stability, which are superior to that of three-dimensional copper single-atom catalysts (Cu-SACs, supported by N/S-codoped carbon framework directly derived from ZIF-8). Furthermore, the zinc-air battery assembled with g-Cu-SACs also exhibits high specific capacity and remarkable cycling lifetime. This work provides a novel strategy to construct highly exposed single-atom catalysts for energy-related applications.

Asymmetric coordination engineering of active centers in MXene-based single atom catalysts for high-performance ECO2RR

Asymmetric coordination effect is an important concept in heterogeneous catalysis where both catalytic activity and product selectivity are serious influenced. However, this effect has rarely been understood because of the difficult in characterizing detailed coordination information. Here, by employing a theoretical study on electrocatalytic CO2 reduction reaction (ECO2RR) towards HCOOH over Ti3C2O2-based NS/NN co-coordinated transition metal single atom catalysts (TM-NS/NN-Ti3C2O2 SACs), we show that asymmetric coordination environments have great impact on the electronic structure of the active center. Both electron transferring ability and spin polarization of the active center are vital to optimize the adsorption and hydrogenation of key intermediates. As a result, both catalytic activity and product selectivity can be maximized. V-NN-Ti3C2O2 are predicted to promote high-throughput HCOOH generation process at operation applied potential of −0.32 with considerable electrochemical stability, surpassing most reported catalysts. This work demonstrates V-NN-Ti3C2O2 as high-performance ECO2RR catalysts, and highlights that the introduction of the concept of asymmetric coordination effect may offer a new insight into the rational design of more efficient SACs.

Highly dispersed carbon-encapsulated FeS/Fe3C nanoparticles distributed in Fe-N-C for enhanced oxygen electrocatalysis and Zn-air batteries

Transition metal single-atom catalysts (SACs) have been widely used in oxygen reduction reactions (ORR) and oxygen evolution reaction (OER) due to its greatest atomic utilization and low costs, which catalytic performance can be further enhanced by electron distribution adjustment. Herein, we synthesized a carbon-encapsulated FeS/Fe3C nanoparticles doped carbon-based Fe single atom catalyst from fluid catalytic cracking (FCC) slurry though a one-pot pyrolysis. The synergistic effect between FeS/Fe3C nanoparticles and Fe single atom structure (FeNx) promotes the ORR/OER processes, which may due to the reduction of the adsorption free energy of intermediates. Meanwhile, the polyaromatic hydrocarbon in FCC slurry enhances the graphitization of catalyst to facilitate charge transfer in electrocatalysis process, and the carbon-encapsulated nanoparticles sites possess higher stability and dispersion. As a result, the optimized catalyst (FeS/Fe3C@Fe-N-C) presents a high nanoparticles dispersion and graphitization level, which has a higher ORR catalytic ability (E1/2 = 0.91 V vs RHE) compared with commercial Pt/C (20 wt%, E1/2 = 0.879 V vs RHE) and a similar OER catalytic ability (E10 = 0.1.506 V vs RHE) compared with RuO2 (E10 = 1.518 V vs RHE). A liquid Zn-air battery assembled with FeS/Fe3C@Fe-N-C show a peak power density of 113 mW cm−2 and an open potential of 1.432 V. This work sheds light on a new method to design transition metal active sites carbon based single-atom catalyst for enhanced ORR and OER processes.

Theoretical design of bifunctional single-atom catalyst over g-C2N2 for oxygen evolution and reduction reactions

The two-dimensional graphitic carbon nitride (g-CxNy) is a promising support for electrochemistry catalysts owing to its stability and controllable chemical composition. Here, by density functional theory (DFT) a serial of transition metal single-atom catalysts (SAC) supported on the g-C2N2 with vacancy (denoted as TM1/C2N2, TM=Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir and Pt) were studied for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). The non-noble Ni and Co single atom exhibited relatively strong binding energies over the defective g-C2N2 support. The d-band center of TM performed a good descriptor for adsorption free energies of intermediates. For OER, the overpotential of non-noble Co1/C2N2 was as low as 0.30 V, comparable to Rh1/C2N2. For ORR, both Co1/C2N2 and Rh1/C2N2 displayed excellent performance with overpotentials of around 0.50 V. The volcano plot revealed that the proper binding strength of O* and OH* on Co1/C2N2 rendered it an excellent bifunctional catalyst for both OER and ORR. Considering the superior performance of Co SAC over g-C2N2 than not only g-C3N4 but also defective graphene, we postulate that there could exist an optimized C/N ratio of carbon-rich g-CxNy support for improving the non-noble Co SAC activity on oxygen electrode.

Screening of transition metal dual-atom catalysts for hydrogen evolution reaction based on high-throughput calculation and searching surrogate prediction model using simple features

Dual-atom catalysts for hydrogen evolution reaction have received widespread attention, but precise screening and prediction of high-performance catalysts through simple methods remains a challenge. In this study, we perform high-throughput density functional theory (DFT) calculation and machine learning (ML) to screen and predict the transition metal dual-atom catalysts with N-doped graphene support (TMDACs) for acidic hydrogen evolution reaction (HER). The Fe_Zn and V_Fe DACs were proposed to be the most promising candidates for Pt-based catalyst toward acidic HER from 406 TMDACs, based on the characteristics of HER activity, formation, thermodynamic stability, abundance, environmental friendliness. The Fe_Zn and V_Fe DACs with excellent HER performance is due to the synergistic effect deriving from the interaction between H and dual metal atoms in TMDACs. By determining 6 different ML models with four kind of input features, we find the artificial neural networks (ANN) model can predict the HER performance of TMDACs most accurately only using simple input features, including one-hot-encoding of atomic number and Gibbs free energies of transition metal single-atom catalysts. This work not only proposed the potential TMDACs with high HER performance, but also verified that the ANN model can accurately predict the HER activity of diatomic catalysts with simple input features.

High-throughput screening of N-doped curved graphene-loaded transition metal single-atom catalysts for nitrogen reduction reaction

Nitrogen reduction reaction (NRR) is necessary as an environmentally friendly and sustainable method for producing NH3 in the context of the energy crisis and increasing environmental concerns. Efficient catalysts play an important role in the NRR reaction. In this work, a high-curvature tetracoordinate transition metal (TM) nitrogen-doped graphene single-atom catalyst was designed and five candidate catalysts with excellent performances were selected from 406 models through a combination of high-throughput screening and density functional theory calculations. Using seven different coordination types MC4, MC3N1, MC2N2-1, MC2N2-2, MC2N2-3, MC1N3 and MN4, of which VN4 (side-on) with four N-atom coordination has the lowest limiting potential of 0.31 V and the competing Hydrogen Evolution Reaction (HER) was suppressed. This work provides guidance for the development of efficient NRR catalysts.

Turning natural copper phthalocyanine into high-loading single-atom catalysts using an electrochemically-generated template and cationic substitution

Phthalocyanine (PC) has a unique N4-coordinated structure that offers an inherent advantage with respect to the accommodation of metal ions. This feature can help overcome the limitations of many single-atom electrocatalysts, i.e. low loading and poor stability. Here, we detail the development of a universal electrochemical template and a cationic substitution synthesis protocol for preparing various single-atom catalysts with high-loading (≌ 8.6 wt%) from commercial copper phthalocyanine (CuPC). Commercial CuPC is transformed into Cu NPs and vacant N4-sites are created during applied potential cycling. The generated vacant N4-sites, with strong negative charges, can take-up Pd2+ ions from a precursor solution to create single-atom catalysts with Pd high-loadings. The material’s structural transformation and cationic substitution mechanism were investigated by in situ X-ray absorption spectroscopy (XAS). We also demonstrate the viability of extending the proposed electrochemical template synthesis method to the development of other high-loading transition metal single-atom catalysts, e.g., Ni, Co, and Fe.

In situ Activation of Molecular Oxygen at Intermetallic Spacing-Optimized Iron Network-Like Sites for Boosting Electrocatalytic Oxygen Reduction.

The oxygen reduction reaction (ORR) catalyzed by transition-metal single-atom catalysts (SACs) is promising for practical applications in energy-conversion devices, but great challenges still remain due to the sluggish kinetics of O═O cleavage. Herein, a kind of high-density iron network-like sites catalysts are constructed with optimized intermetallic distances on an amino-functionalized carbon matrix (Fe-HDNSs). Quasi-in situ soft X-ray absorption spectroscopy and in situ synchrotron infrared characterizations demonstrate that the optimized intermetallic distances in Fe-HDNSs can in situ activate the molecular oxygen by fast electron compensation through the hybridized Fe 3d-O 2p, which efficiently facilitates the cleavage of the O═O bond to *O species and highly suppresses the side reactions for an accelerated kinetics of the 4e- ORR. As a result, the well-designed Fe-HDNSs catalysts exhibit superior performances with a half-wave potential of 0.89V versus reversible hydrogen electrode (RHE)and a kinetic current density of 72mAcm-2 @0.80V versus RHE, exceeding most of the noble-metal-free ORR catalysts. This work offers some new insights into the understanding of 4e- ORR kinetics and reaction pathways to boost electrochemical performances of SACs.

The recent progress of cathode materials for heterogeneous electro-Fenton reactions

As one of environmentally friendly and efficient oxidation techniques, the electro-Fenton (EF) processes allow to remove and mineralize organic pollutants. However, the transitional EF processes require an acidic environment, adding ferrous ions, treatment of iron sludge, and costly solution pH adjustment. Heterogeneous EF (hetero-EF) processes enable EF to function over a broad working pH region and recycle across multiple reaction rounds which reduces overall cost and displays great potential for practical engineering applications. Here, this work reviewed the reported cathode materials for the hetero-EF processes. We firstly described the mechanisms of homogeneous and heterogeneous EF reactions. Then, we summarized different types of cathode materials for hetero-EF reactions, including metal-free carbon materials, transition metal single-atom catalysts (SACs)/carbon materials, alloys catalysts/carbon materials, metal compounds/carbon materials and other materials. Finally, we overviewed the challenges and proposal strategies of hetero-EF technique in order to expand its wide-scale applicability and practical significance for advanced wastewater treatment.

Quantum chemical studies of transition metal single-atom catalysts: exploration of catalytic descriptors

This work provides important insight into the structure–activity relationships of transition metal single-atom catalysts. Various traditional, spectral and electronic descriptors are suggested.

Computational screening of defective BC3-supported single-atom catalysts for electrochemical CO2 reduction.

The electrochemical CO2 reduction reaction (eCO2RR) driven by renewable electricity offers a green and sustainable technology for synthesizing chemicals and managing global carbon balance. However, developing electrocatalysts with high activity and selectivity for producing C1 products (CO, HCOOH, CH3OH, and CH4) remains a daunting task. In this study, we conducted comprehensive first-principles calculations to investigate the eCO2RR mechanism using B-defective BC3-supported transition metal single-atom catalysts (TM@BC3 SACs). Initially, we evaluated the thermodynamic and electrochemical stability of the designed 26 TM@BC3 SACs by calculating the binding energy and dissolution potential of the anchored TM atoms. Subsequently, the selectivity of the eCO2RR and hydrogen evolution reaction (HER) on stable SACs was determined by comparing the free energy change (ΔG) for the first protonation of CO2 with the ΔG of *H formation. The stability and selectivity screening processes enabled us to narrow down the pool of SACs to the 14 promising ones. Finally, volcano plots for the eCO2RR towards different C1 products were established by using the adsorption energy descriptors of key intermediates, and three SACs were predicted to exhibit high activity and selectivity. The limiting potentials (UL) for HCOOH production on Pd@BC3 and Ag@BC3 are -0.11 V and -0.14 V. CH4 is a preferred product on Re@BC3 with UL of -0.22 V. Elaborate electronic structure calculations elucidate that the activity and selectivity originate from the sufficient activation of the C-O bond and the strong orbital hybridization between crucial intermediates and metal atoms. The proposed catalyst screening criteria, constructed volcano plots and predicted SACs may provide a theoretical foundation for the development of computationally guided catalyst designs for electrochemical CO2 conversion to C1 products.

Mechanistic insights into high-throughput screening of tandem catalysts for CO2 reduction to multi-carbon products.

In carbon dioxide electrochemical reduction (CO2ER), since isolated catalysts encounter challenges in meeting the demands of intricate processes for producing multi-carbon (C2+) products, tandem catalysis is emerging as a promising approach. Nevertheless, there remains an insufficient theoretical understanding of designing tandem catalysts. Herein, we utilized density functional theory (DFT) to screen 80 tandem catalysts for efficient CO2ER to C2 products systematically, which combines the advantages of nitrogen-doped carbon-supported transition metal single-atom catalysts (M-N-C) and copper clusters. Three crucial criteria were designed to select structures for generation and transfer of *CO and facilitate C-C coupling. The optimal Cu/RuN4-pl catalyst exhibited an excellent ethanol production capacity. Additionally, the relationship between CO adsorption strength and transfer energy barrier was established, and the influence of the electronic structure on its adsorption strength was studied. This provided a novel and well-considered solution and theoretical guidance for the design of rational composition and structurally superior tandem catalysts.

Emerging electrospinning platform toward nanoparticle to single atom transformation for steering selectivity in ammonia synthesis.

The rising top-down synthetic methodologies for transition metal single-atom catalysts (SACs) require controlled movement of metal atoms through the substrates; however, their direct transportation towards the ideal carrier remains a huge challenge. Herein, we showed a "top down" strategy for Co nanoparticles (NPs) to Co SA transformation by employing electrospun carbon nanofibers (CNFs) as atom carriers. Under high-temperature conditions, the Co atoms migrate from the surfaces of Co NPs and are then anchored by the surrounding carbon to form a Co-C3O1 coordination structure. The synthesized Co SAs/CNF electrocatalyst exhibits excellent electrocatalytic nitrate reduction reaction (NO3RR) activity with an NH3 yield of 0.79 mmol h-1 cm-2 and Faraday efficiency (FE) of 91.3% at -0.7 V vs. RHE in 0.1 M KNO3 and 0.1 M K2SO4 electrolytes. The in situ electrochemical characterization suggests that the NOH pathway is preferred by Co SAs/CNFs, and *NO hydrogenation and deoxygenation easily occur on Co SAs due to the small adsorption energy between Co SAs and *NO, as calculated by theoretical calculations. It is revealed that a small energy barrier (0.45 eV) for the rate determining step (RDS) ranges from *NO to *NOH and a strong capability for inhibiting hydrogen evolution (HER) significantly promotes the NH3 selectivity and activity of Co SAs/CNFs.

Design strategies towards transition metal single atom catalysts for the oxygen reduction reaction – A review

The electrochemical oxygen reduction reaction (ORR) is pivotal in energy conversion <i>via</i> a 4e⁻ ORR pathway and green hydrogen peroxide production <i>via</i> 2e⁻ ORR pathway. Transition metal single atom catalysts (TM SACs) have attracted intense attention in recent years for ORR due to their high activity and near maximum metal atom utilization. The future development of TM SACs for ORR requires improved understanding of reaction pathways, since currently the true origin of activity remains contentious owing to the lack of qualitative/quantitative information about active sites. Knowledge-guided design is imperative for the optimization of TM SACs performance in terms of activity and selectivity. This review focuses on the latest progress in the design of TM SACs for ORR, placing particular attention on efforts to elucidate reaction mechanisms. Experimental evidence based on <i>in-situ/operando</i> characterization measurements, along with theoretical predictions, are summarized to deepen understanding of the structure-performance relationships at both atomic and molecular level. Finally, some perspectives are offered relating to the fundamental science needed for TM SACs to find practical application in energy storage and conversion devices. We hope this review will inspire the development of new synthetic routes towards high-performance ORR electrocatalysts for the energy sector.