Fenton-like activity and pathway modulation via single-atom sites and pollutants comediates the electron transfer process.

The studies on the origin of versatile oxidation pathways toward targeted pollutants in the single-atom catalysts (SACs)/peroxymonosulfate (PMS) systems were always associated with the coordination structures rather than the perspective of pollutant characteristics, and the analysis of mechanism commonality is lacking. In this work, a variety of single-atom catalysts (M-SACs, M: Fe, Co, and Cu) were fabricated via a pyrolysis process using lignin as the complexation agent and substrate precursor. Sixteen kinds of commonly detected pollutants in various references were selected, and their lnkobs values in M-SACs/PMS systems correlated well (R2 = 0.832 to 0.883) with their electrophilic indexes (reflecting the electron accepting/donating ability of the pollutants) as well as the energy gap (R2 = 0.801 to 0.840) between the pollutants and M-SACs/PMS complexes. Both the electron transfer process (ETP) and radical pathways can be significantly enhanced in the M-SACs/PMS systems, while radical oxidation was overwhelmed by the ETP oxidation toward the pollutants with lower electrophilic indexes. In contrast, pollutants with higher electrophilic indexes represented the weaker electron-donating capacity to the M-SACs/PMS complexes, which resulted in the weaker ETP oxidation accompanied with noticeable radical oxidation. In addition, the ETP oxidation in different M-SACs/PMS systems can be regulated via the energy gaps between the M-SACs/PMS complexes and pollutants. As a result, the Fenton-like activities in the M-SACs/PMS systems could be well modulated by the reaction pathways, which were determined by both electrophilic indexes of pollutants and single-atom sites. This work provided a strategy to establish PMS-based AOP systems with tunable oxidation capacities and pathways for high-efficiency organic decontamination.

Precise coordination of high-loading Fe single atoms with sulfur boosts selective generation of nonradicals.

Nonradicals are effective in selectively degrading electron-rich organic contaminants, which unfortunately suffer from unsatisfactory yield and uncontrollable composition due to the competitive generation of radicals. Herein, we precisely construct a local microenvironment of the carbon nitride-supported high-loading (~9 wt.%) Fe single-atom catalyst (Fe SAC) with sulfur via a facile supermolecular self-assembly strategy. Short-distance S coordination boosts the peroxymonosulfate (PMS) activation and selectively generates high-valent iron-oxo species (FeIV=O) along with singlet oxygen (1O2), significantly increasing the 1O2 yield, PMS utilization, and p-chlorophenol reactivity by 6.0, 3.0, and 8.4 times, respectively. The composition of nonradicals is controllable by simply changing the S content. In contrast, long-distance S coordination generates both radicals and nonradicals, and could not promote reactivity. Experimental and theoretical analyses suggest that the short-distance S upshifts the d-band center of the Fe atom, i.e., being close to the Fermi level, which changes the binding mode between the Fe atom and O site of PMS to selectively generate 1O2 and FeIV=O with a high yield. The short-distance S-coordinated Fe SAC exhibits excellent application potential in various water matrices. These findings can guide the rational design of robust SACs toward a selective and controllable generation of nonradicals with high yield and PMS utilization.

Enhancing the activity of Pd ensembles on graphene by manipulating coordination environment.

Atomic dispersion of metal catalysts on a substrate accounts for the increased atomic efficiency of single-atom catalysts (SACs) in various catalytic schemes compared to the nanoparticle counterparts. However, lacking neighboring metal sites has been shown to deteriorate the catalytic performance of SACs in a few industrially important reactions, such as dehalogenation, CO oxidation, and hydrogenation. Metal ensemble catalysts (Mn), an extended concept to SACs, have emerged as a promising alternative to overcome such limitation. Inspired by the fact that the performance of fully isolated SACs can be enhanced by tailoring their coordination environment (CE), we here evaluate whether the CE of Mn can also be manipulated in order to enhance their catalytic activity. We synthesized a set of Pd ensembles (Pdn) on doped graphene supports (Pdn/X-graphene where X = O, S, B, and N). We found that introducing S and N onto oxidized graphene modifies the first shell of Pdn converting Pd-O to Pd-S and Pd-N, respectively. We further found that the B dopant significantly affected the electronic structure of Pdn by serving as an electron donor in the second shell. We examined the performance of Pdn/X-graphene toward selective reductive catalysis, such as bromate reduction, brominated organic hydrogenation, and aqueous-phase CO2 reduction. We observed that Pdn/N-graphene exhibited superior performance by lowering the activation energy of the rate-limiting step, i.e., H2 dissociation into atomic hydrogen. The results collectively suggest controlling the CE of SACs in an ensemble configuration is a viable strategy to optimize and enhance their catalytic performance.

Single-atom Mo-Co catalyst with low biotoxicity for sustainable degradation of high-ionization-potential organic pollutants.

Single-atom catalysts (SACs) are a promising area in environmental catalysis. We report on a bimetallic Co-Mo SAC that shows excellent performance in activating peroxymonosulfate (PMS) for sustainable degradation of organic pollutants with high ionization potential (IP > 8.5 eV). Density Functional Theory (DFT) calculations and experimental tests demonstrate that the Mo sites in Mo-Co SACs play a critical role in conducting electrons from organic pollutants to Co sites, leading to a 19.4-fold increase in the degradation rate of phenol compared to the CoCl2-PMS group. The bimetallic SACs exhibit excellent catalytic performance even under extreme conditions and show long-term activation in 10-d experiments, efficiently degrading 600 mg/L of phenol. Moreover, the catalyst has negligible toxicity toward MDA-MB-231, Hela, and MCF-7 cells, making it an environmentally friendly option for sustainable water treatment. Our findings have important implications for the design of efficient SACs for environmental remediation and other applications in biology and medicine.

Free-standing membrane incorporating single-atom catalysts for ultrafast electroreduction of low-concentration nitrate.

The release of wastewaters containing relatively low levels of nitrate (NO3-) results in sufficient contamination to induce harmful algal blooms and to elevate drinking water NO3- concentrations to potentially hazardous levels. In particular, the facile triggering of algal blooms by ultra-low concentrations of NO3- necessitates the development of efficient methods for NO3- destruction. However, promising electrochemical methods suffer from weak mass transport under low reactant concentrations, resulting in long treatment times (on the order of hours) for complete NO3- destruction. In this study, we present flow-through electrofiltration via an electrified membrane incorporating nonprecious metal single-atom catalysts for NO3- reduction activity enhancement and selectivity modification, achieving near-complete removal of ultra-low concentration NO3- (10 mg-N L-1) with a residence time of only a few seconds (10 s). By anchoring Cu single atoms supported on N-doped carbon in a carbon nanotube interwoven framework, we fabricate a free-standing carbonaceous membrane featuring high conductivity, permeability, and flexibility. The membrane achieves over 97% NO3- removal with high N2 selectivity of 86% in a single-pass electrofiltration, which is a significant improvement over flow-by operation (30% NO3- removal with 7% N2 selectivity). This high NO3- reduction performance is attributed to the greater adsorption and transport of nitric oxide under high molecular collision frequency coupled with a balanced supply of atomic hydrogen through H2 dissociation during electrofiltration. Overall, our findings provide a paradigm of applying a flow-through electrified membrane incorporating single-atom catalysts to improve the rate and selectivity of NO3- reduction for efficient water purification.

Boosted ammonium production by single cobalt atom catalysts with high Faradic efficiencies.

Efficient n = O bond activation is crucial for the catalytic reduction of nitrogen compounds, which is highly affected by the construction of active centers. In this study, n = O bond activation was achieved by a single-atom catalyst (SAC) with phosphorus anchored on a Co active center to form intermediate N-species for further hydrogenation and reduction. Unique phosphorus-doped discontinuous active sites exhibit better n = O activation performance than conventional N-cooperated single-atom sites, with a high Faradic efficiency of 92.0% and a maximum ammonia yield rate of 433.3 µg NH4·h-1·cm-2. This approach of constructing environmental sites through heteroatom modification significantly improves atom efficiency and will guide the design of future functional SACs with wide-ranging applications.

Achieving complete electrooxidation of ethanol by single atomic Rh decoration of Pt nanocubes.

SignificanceDirect ethanol fuel cells are attracting growing attention as portable power sources due to their advantages such as higher mass-energy density than hydrogen and less toxicity than methanol. However, it is challenging to achieve the complete electrooxidation to generate 12 electrons per ethanol, resulting in a low fuel utilization efficiency. This manuscript reports the complete ethanol electrooxidation by engineering efficient catalysts via single-atom modification. The combined electrochemical measurements, in situ characterization, and density functional theory calculations unravel synergistic effects of single Rh atoms and Pt nanocubes and identify reaction pathways leading to the selective C-C bond cleavage to oxidize ethanol to CO2. This study provides a unique single-atom approach to tune the activity and selectivity toward complicated electrocatalytic reactions.

Electron Deficient Ir-O Bonds Promote Heterogeneous Ir-Catalyzed Anti-Markovnikov Hydroboration of Alkenes under Mild Neat Conditions.

Tuning electronic characteristics of metal-ligand bonds based on reaction pathways to achieve efficient catalytic processes has been widely studied and proven to be feasible in homogeneous catalysis, but it is scarcely investigated in heterogeneous catalysis. Herein, we demonstrate the regulation of the electronic configuration of Ir-O bonds in an Ir single-atom catalyst according to the borane activation mechanism. Ir-O bonds in Ir1/Ni(OH)x are found to be more electron-poor than those in Ir1/NiOx. Despite the mild solvent-free conditions and ambient temperature, Ir1/Ni(OH)x exhibits outstanding performance for the hydroboration of alkenes, furnishing the desired alkylboronic esters with a turnover frequency value of ≤3060 h-1 and 99% anti-Markovnikov selectivity, which is significantly better than that of Ir1/NiOx (42 h-1). It is further proven that the more electron-poor Ir-O bonds as active centers are more oxidative and so benefit the activation of the H-B bond in the reductive pinacolborane.

Enhancing Haloarene Coupling Reaction Efficiency on an Oxide Surface by Metal Atom Addition.

The bottom-up synthesis of carbon-based nanomaterials directly on semiconductor surfaces allows for the decoupling of their electronic and magnetic properties from the substrates. However, the typically reduced reactivity of such nonmetallic surfaces adversely affects the course of these reactions. Here, we achieve a high polymerization yield of halogenated polyphenyl molecular building blocks on the semiconducting TiO2(110) surface via concomitant surface decoration with cobalt atoms, which catalyze the Ullmann coupling reaction. Specifically, cobalt atoms trigger the debromination of 4,4″-dibromo-p-terphenyl molecules on TiO2(110) and mediate the formation of an intermediate organometallic phase already at room temperature (RT). As the debromination temperature is drastically reduced, homocoupling and polymerization readily proceed, preventing presursor desorption from the substrate and entailing a drastic increase of the poly-para-phenylene polymerization yield. The general efficacy of this mechanism is shown with an iodinated terphenyl derivative, which exhibits similar dehalogenation and reaction yield.

Zn Single-Atom Catalysts Enable the Catalytic Transfer Hydrogenation of α,ß-Unsaturated Aldehydes.

Highly active nonprecious-metal single-atom catalysts (SACs) toward catalytic transfer hydrogenation (CTH) of α,ß-unsaturated aldehydes are of great significance but still are deficient. Herein, we report that Zn-N-C SACs containing Zn-N3 moieties can catalyze the conversion of cinnamaldehyde to cinnamyl alcohol with a conversion of 95.5% and selectivity of 95.4% under a mild temperature and atmospheric pressure, which is the first case of Zn-species-based heterogeneous catalysts for the CTH reaction. Isotopic labeling, in situ FT-IR spectroscopy, and DFT calculations indicate that reactants, coabsorbed at the Zn sites, proceed CTH via a "Meerwein-Ponndorf-Verley" mechanism. DFT calculations also reveal that the high activity over Zn-N3 moieties stems from the suitable adsorption energy and favorable reaction energy of the rate-determining step at the Zn active sites. Our findings demonstrate that Zn-N-C SACs hold extraordinary activity toward CTH reactions and thus provide a promising approach to explore the advanced SACs for high-value-added chemicals.

Catalytic Potential of Supported Superatoms.

The importance of catalysts in industrial products is a driving factor in the search of efficient and cost-effective catalysts, creating considerable interest in the past decade in single-atom catalysis. One of the first requirements of a good catalyst is that it should bind to the molecules with energies intermediate between physisorption and chemisorption while simultaneously activating them. Herein, it is shown that superatoms, which are atomic clusters with fixed size and composition, can meet this challenge even better than the atoms whose chemistry they mimic. The reactions of molecules such as H2, O2, N2, CO, NO, and CO2 with an atom (Li) and its corresponding superatom (Li3O) are confirmed through study. As these clusters need to be supported on a substrate for practical applications, the study focuses on the reaction of CO2 with Li and Li3O supported on graphene, Au(111), and Cu(111) substrates. Using density functional theory, it is shown that the Li3O superatom can activate CO2 far greater than the Li atom - stretching the CO bond from 1.16 Å to as large as 1.30 Å and bending the O─C─O bond angle from 180° to as low as 120°. Equally interesting, the results are not very sensitive to the substrate.

Pyrolysis Free Out-of-Plane Co-Single Atomic Sites in Porous Organic Photopolymer Stimulates Solar-Powered CO2 Fixation.

Herein, a facile strategy is illustrated to develop pyrolysis-free out-of-plane coordinated single atomic sites-based M-POP via a one-pot Friedel Craft acylation route followed by a post-synthetic metalation. The optimized geometry of the Co@BiPy-POP clearly reveals the presence of out-of-plane Co-single atomic sites in the porous backbone. This novel photopolymer Co@BiPy-POP shows extensive π-conjugations followed by impressive light harvesting ability and is utilized for photochemical CO2 fixation to value-added chemicals. A remarkable conversion of styrene epoxide (STE) to styrene carbonate (STC) (≈98%) is obtained under optimized photocatalytic conditions in the existence of promoter tert-butyl ammonium bromide (TBAB). Synchrotron-based X-ray adsorption spectroscopy (XAS) analysis reveals the single atom coordination sites along with the metal (Co) oxidation number of +2.16 in the porous network. Moreover, in situ diffuse reflectance spectroscopy (DRIFTS) and electron paramagnetic resonance (EPR) investigations provide valuable information on the evolution of key reaction intermediates. Comprehensivecomputational analysis also helps to understand the overall mechanistic pathway along with the interaction between the photocatalyst and reactants. Overall, this study presents a new concept of fabricating porous photopolymers based on a pyrolysis-free out-of-plane-coordination strategy and further explores the role of single atomic sites in carrying out feasible CO2 fixation reactions.

Optimization of Carbon-Defect Engineering to Boost Catalytic Ozonation Efficiency of Single Fe─N4 Coordination Motif.

Carbon-defect engineering in single-atom metal-nitrogen-carbon (M─N─C) catalysts by straightforward and robust strategy, enhancing their catalytic activity for volatile organic compounds, and uncovering the carbon vacancy-catalytic activity relationship are meaningful but challenging. In this study, an iron-nitrogen-carbon (Fe─N─C) catalyst is intentionally designed through a carbon-thermal-diffusion strategy, exposing extensively the carbon-defective Fe─N4 sites within a micro-mesoporous carbon matrix. The optimization of Fe─N4 sites results in exceptional catalytic ozonation efficiency, surpassing that of intact Fe─N4 sites and commercial MnO2 by 10 and 312 times, respectively. Theoretical calculations and experimental data demonstrated that carbon-defect engineering induces selective cleavage of C─N bond neighboring the Fe─N4 motif. This induces an increase in non-uniform charges and Fermi density, leading to elevated energy levels at the center of Fe d-band. Compared to the intact atomic configuration, carbon-defective Fe─N4 site is more activated to strengthen the interaction with O3 and weaken the O─O bond, thereby reducing the barriers for highly active surface atomic oxygen (*O/*OO), ultimately achieving efficient oxidation of CH3SH and its intermediates. This research not only offers a viable approach to enhance the catalytic ozonation activity of M─N─C but also advances the fundamental comprehension of how periphery carbon environment influences the characteristics and efficacy of M─N4 sites.

Sulfur Modified Carbon-Based Single-Atom Catalysts for Electrocatalytic Reactions.

Efficient and sustainable energy development is a powerful tool for addressing the energy and environmental crises. Single-atom catalysts (SACs) have received high attention for their extremely high atom utilization efficiency and excellent catalytic activity, and have broad application prospects in energy development and chemical production. M-N4 is an active center model with clear catalytic activity, but its catalytic properties such as catalytic activity, selectivity, and durability need to be further improved. Adjustment of the coordination environment of the central metal by incorporating heteroatoms (e.g., sulfur) is an effective and feasible modification method. This paper describes the precise synthetic methods for introducing sulfur atoms into M-N4 and controlling whether they are directly coordinated with the central metal to form a specific coordination configuration, the application of sulfur-doped carbon-based single-atom catalysts in electrocatalytic reactions such as ORR, CO2RR, HER, OER, and other electrocatalytic reaction are systematically reviewed. Meanwhile, the effect of the tuning of the electronic structure and ligand configuration parameters of the active center due to doped sulfur atoms with the improvement of catalytic performance is introduced by combining different characterization and testing methods. Finally, several opinions on development of sulfur-doped carbon-based SACs are put forward.

Advancements in Electrocatalytic Nitrogen Reduction: A Comprehensive Review of Single-Atom Catalysts for Sustainable Ammonia Synthesis.

Electrocatalytic nitrogen reduction technology seamlessly aligns with the principles of environmentally friendly chemical production. In this paper, a comprehensive review of recent advancements in electrocatalytic NH3 synthesis utilizing single-atom catalysts (SACs) is offered. Into the research and applications of three categories of SACs: noble metals (Ru, Au, Rh, Ag), transition metals (Fe, Mo, Cr, Co, Sn, Y, Nb), and nonmetallic catalysts (B) in the context of electrocatalytic ammonia synthesis is delved. In-depth insights into the material preparation methods, single-atom coordination patterns, and the characteristics of the nitrogen reduction reaction (NRR) are provided. The systematic comparison of the nitrogen reduction capabilities of various SAC types offers a comprehensive research framework for their integration into electrocatalytic NRR. Additionally, the challenges, potential solutions, and future prospects of incorporating SACs into electrocatalytic nitrogen reduction endeavors are discussed.

Single Transition-Metal Atom Anchored on a Rhenium Disulfide Monolayer: An Efficient Bifunctional Electrocatalyst for the Oxygen Evolution and Oxygen Reduction Reactions.

Developing efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) bifunctional electrocatalysts is attractive for rechargeable metal-air batteries. Meanwhile, single metal atoms embedded in 2D layered transition metal chalcogenides (TMDs) have become a very promising catalyst. Recently, many attentions have been paid to the 2D ReS2 electrocatalyst due to its unique distorted octahedral 1T' crystal structure and thickness-independent electronic properties. Here, the catalytic activity of different transition metal (TM) atoms embedded in ReS2 using the density functional theory is investigated. The results indicate that TM@ReS2 exhibits outstanding thermal stability, good electrical conductivity, and electron transfer for electrochemical reactions. And the Ir@ReS2 and Pd@ReS2 can be used as OER/ORR bifunctional electrocatalysts with a lower overpotential for OER (ηOER) of 0.44 V and overpotentials for ORR (ηORR) of 0.26 V and 0.27 V, respectively. The excellent catalytic activity is attributed to the optimal adsorption strength for oxygen intermediates coming from the effective modulation of the electronic structure of ReS2 after Ir/Pd doping. The results can help to deeply understand the catalytic activity of TM@ReS2 and develop novel and highly efficient OER/ORR electrocatalysts.

Copper Dispersed Covalent Organic Framework for Azide-Alkyne Cycloaddition and Fast Synthesis of Rufinamide in Water.

A crystalline porous bipyridine-based Bpy-COF with a high BET surface area (1864 m2 g-1) and uniform mesopore (4.0 nm) is successfully synthesized from 1,3,5-tris-(4'-formyl-biphenyl-4-yl)triazine and 5,5'-diamino-2,2'-bipyridine via a solvothermal method. After Cu(I)-loading, the resultant Cu(I)-Bpy-COF remained the ordered porous structure with evenly distributed Cu(I) ions at a single-atom level. Using Cu(I)-Bpy-COF as a heterogeneous catalyst, high conversions for cycloaddition reactions are achieved within a short time (40 min) at 25 °C in water medium. Moreover, Cu(I)-Bpy-COF proves to be applicable for aromatic and aliphatic azides and alkynes bearing various substituents such as ester, hydroxyl, amido, pyridyl, thienyl, bulky triphenylamine, fluorine, and trifluoromethyl groups. The high conversions remain almost constant after five cycles. Additionally, the antiepileptic drug (rufinamide) is successfully prepared by a simple one-step reaction using Cu(I)-Bpy-COF, proving its practical feasibility for pharmaceutical synthesis.

Single-Atom Co─O4 Sites Embedded in a Defective-Rich Porous Carbon Layer for Efficient H2O2 Electrosynthesis.

The production of hydrogen peroxide (H2O2) via the two-electron electrochemical oxygen reduction reaction (2e- ORR) is an essential alteration in the current anthraquinone-based method. Herein, a single-atom Co─O4 electrocatalyst is embedded in a defective and porous graphene-like carbon layer (Co─O4@PC). The Co─O4@PC electrocatalyst shows promising potential in H2O2 electrosynthesis via 2e- ORR, providing a high H2O2 selectivity of 98.8% at 0.6 V and a low onset potential of 0.73 V for generating H2O2. In situ surface-sensitive attenuated total reflection Fourier transform infrared spectra and density functional theory calculations reveal that the electronic and geometric modification of Co─O4 induced by defective carbon sites result in decreased d-band center of Co atoms, providing the optimum adsorption energies of OOH* intermediate. The H-cell and flow cell assembled using Co─O4@PC as the cathode present long-term stability and high efficiency for H2O2 production. Particularly, a high H2O2 production rate of 0.25 mol g-1 cat h-1 at 0.6 V can be obtained by the flow cell. The in situ-generated H2O2 can promote the degradation of rhodamine B and sterilize Staphylococcus aureus via the Fenton process. This work can pave the way for the efficient production of H2O2 by using Co─O4 single atom electrocatalyst and unveil the electrocatalytic mechanism.

Theoretical Insight into the Special Synergy of Bimetallic Site in Co/MoC Catalyst to Promote N2 -to-NH3 Conversion.

The catalytic mechanisms of nitrogen reduction reaction (NRR) on the pristine and Co/α-MoC(001) surfaces were explored by density functional theory calculations. The results show that the preferred pathway is that a direct N≡N cleavage occurs first, followed by continuous hydrogenations. The production of second NH3 molecule is identified as the rate-limiting step on both systems with kinetic barriers of 1.5 and 2.0 eV, respectively, indicating that N2 -to-NH3 transformation on bimetallic surface is more likely to occur. The two components of the bimetallic center play different roles during NRR process, in which Co atom does not directly participate in the binding of intermediates, but primarily serves as a reservoir of H atoms. This special synergy makes Co/α-MoC(001) have superior activity for ammonia synthesis. The introduction of Co not only facilitates N2 dissociation, but also accelerates the migration of H atom due to the antibonding characteristic of Co-H bond. This study offers a facile strategy for the rational design and development of efficient catalysts for ammonia synthesis and other reactions involving the hydrogenation processes.

Electroreduction of CO2 on Cu, Fe, or Ni-doped Diamane Sheets: A DFT Study.

Poor mass transfer behavior and inherent activity limit the efficiency of traditional catalysts in electrocatalyzing carbon dioxide reduction reactions. However, the development of novel nanomaterials provides new strategies to solve the above problems. Herein, we propose novel single-metal atom catalysts, namely diamane-based electrocatalysts doped with Cu, Fe, and Ni, explored through density functional theory (DFT) calculations. We thoroughly investigated the doping pattern and energetics for different dopants. Furthermore, we systematically investigated the conversion process of CO2 to C1 or C2+ products, utilizing the free energy analysis of reaction pathways. Our results reveal that dopants could only be introduced into diamane following a specific pattern. Dopants significantly enhance the CO2 adsorption ability of diamane, with Fe and Ni proving notably more effective than Cu. After CO2 adsorption, Cu- and Fe-doped diamane prefer to catalyze CO2RR, while Ni-doped diamane favors hydrogen evolution reaction (HER). The C-C coupling reaction on Cu-hollow diamane, Cu-bridge diamane, and Fe-hollow diamane tends to be from C2+ products. Among all examined catalysts, Cu-hollow diamane shows better electro-catalytic performance. Our study demonstrates the feasibility of and contributes to the development of diamane-based electro-catalysts for CO2RR.