Electron-deficient Species Research Articles

Stabilisation of Bromenium Ions in Macrocyclic Halogen Bond Complexes.

Halenium ions (X+) are highly reactive electron deficient species that are prevalent transient intermediates in halogenation reactions. The stabilisation of these species is especially challenging, with the most common approach to sequester reactivity through the formation of bis-pyridine (Py) complexes; [(Py)2X]+. Herein, we present the first example of a macrocyclic stabilisation effect for halenium species. Exploiting a series of bis-pyridine macrocycles, we demonstrate that preorganised macrocyclic ligands stabilise bromenium cations via endotopic complexation, impressively facilitating the isolation of a bench stable 'Br+ NO3 -' species. Solid state X-ray crystallographic structural comparison of macrocyclic Br(I) complexes with Ag(I) and Au(I) analogues provides insightful information concerning similarities and stark contrasts in halenium/metal cation coordination behaviors. Furthermore, the first chemical ligand exchange reactions of Br(I) complexes are reported between acyclic [(Py)2Br]+ species and a bis-pyridine macrocyclic donor ligand which importantly highlights a macrocycle effect for halenium cation stabilisation in the solution phase.

Stabilisation of Bromenium Ions in Macrocyclic Halogen Bond Complexes

AbstractHalenium ions (X+) are highly reactive electron deficient species that are prevalent transient intermediates in halogenation reactions. The stabilisation of these species is especially challenging, with the most common approach to sequester reactivity through the formation of bis‐pyridine (Py) complexes; [(Py)2X]+. Herein, we present the first example of a macrocyclic stabilisation effect for halenium species. Exploiting a series of bis‐pyridine macrocycles, we demonstrate that preorganised macrocyclic ligands stabilise bromenium cations via endotopic complexation, impressively facilitating the isolation of a bench stable ‘Br+ NO3−’ species. Solid state X‐ray crystallographic structural comparison of macrocyclic Br(I) complexes with Ag(I) and Au(I) analogues provides insightful information concerning similarities and stark contrasts in halenium/metal cation coordination behaviors. Furthermore, the first chemical ligand exchange reactions of Br(I) complexes are reported between acyclic [(Py)2Br]+ species and a bis‐pyridine macrocyclic donor ligand which importantly highlights a macrocycle effect for halenium cation stabilisation in the solution phase.

Hydrogen Evolution Reactivity of Pentagonal Carbon Rings and p-d Orbital Hybridization Effect with Ru.

Topological defects are inevitable existence in carbon-based frameworks, but their intrinsic electrocatalytic activity and mechanism remain under-explored. Herein, the hydrogen evolution reaction (HER) of pentagonal carbon-rings is probed by constructing pentagonal ring-rich carbon (PRC), with optimized electronic structures and higher HER activity relative to common hexagonal carbon (HC). Furthermore, to improve the reactivity, we couple Ru clusters with PRC (Ru@PRC) through p-d orbital hybridization between C and Ru atoms, which drives a shortcut transfer of electrons from Ru clusters to pentagonal rings. The electron-deficient Ru species leads to a notable negative shift in d-band centers of Ru and weakens their binding strength with hydrogen intermediates, thus enhancing the HER activity in different pH media. Especially, at a current density of 10 mA cm-2, PRC greatly reduces alkaline HER overpotentials from 540 to 380 mV. And Ru@PRC even exhibits low overpotentials of 28 and 275 mV to reach current densities of 10 and 1000 mA cm-2, respectively. Impressively, the mass activity and price activity of Ru@PRC are 7.83 and 15.7 times higher than that of Pt/C at the overpotential of 50 mV. Our data unveil the positive HER reactivity of pentagonal defects and good application prospects.

Revealing Significant Electronic Effects on the Oxygen Reduction Reaction with Iron Porphyrins.

Understanding electronic effects on catalysis from a mechanism point of view is of fundamental significance but is also challenging. We herein report on electronic effects on the oxygen reduction reaction (ORR) with Fe porphyrins. By using FeIII tetraphenylporphyrin (TPP-Fe) and FeIII tetra(pentafluorophenyl)porphyrin (TPFP-Fe), we showed their different electrochemical and chemical behaviors for ORR. Mechanism studies revealed that the FeIII-superoxo species of TPP-Fe can undergo smooth protonation with trifluoroacetic acid (TFA) but the electron-deficient FeIII-superoxo species of TPFP-Fe cannot be protonated with TFA. The FeIII-superoxo reactivity difference between TPP-Fe and TPFP-Fe is the origin of their different catalytic ORR behaviors.

Fast tailoring the ZIF-8 surface microenvironment at ambient temperature to boost glucose oxidase-like activity of AuNPs for biosensing

Rational design and tailoring of the surface microenvironment surrounding the catalytic sites, such as noble metal nanoparticles, is an effective way to enhance the catalytic activity of mimicking enzymes. However, it remains on-going challenges to regulate the microenvironment of the catalytic sites due to the lack of tunable variability in structural precision of conventional solid catalysts. Herein, three types of zeolitic imidazolate framework-8 (ZIF-8) with different major crystal facet orientations, i.e., cubic with (100) facets (denoted ZIF-8c), truncated dodecahedral with (100), (110) facets (denoted ZIF-8tr), and dodecahedral with (110) facets (denoted ZIF-8r), were developed facilely using an electrochemical method by switching the potential at ambient temperature. Because the Zn2+ nodes were predominantly exposed on the (100) facets of ZIF-8, while the ligands were mainly exposed on the (110) facets. Hence, gold nanoparticles (AuNPs) showed differential glucose oxidase (GOx)-like activities when anchored in situ on different crystal facets of ZIF-8 and obeyed the following order ZIF-8c/Au>ZIF-8tr/Au>ZIF-8r/Au. Notably, both the metal nodes and aromatic linkers of ZIF-8 interacted with AuNPs through coordination and π-π interactions. The Zn2+ nodes facilitated the formation of the electron-deficient Au species. The electron transfer from AuNPs to Zn2+ sites effectively boosted the catalytic activity. It was known that directly tailoring the microenvironment at the supporting sites of noble metal catalysts to boost catalysis through a facile electrochemical method was not reported. Based on the favorable GOx-like activity and long-term stability of ZIF-8tr/Au, a highly sensitive electrochemical biosensing platform for assaying squamous cell carcinoma antigen (SCCA) was developed. It enabled fg-level detection of cancer marker.

Schiff base-stabilized electron-deficient copper species on MOFs as durable sensor of nitrate in water

The electrochemical sensor has been considered an efficient and portable platform for the rapid quantification of nitrate ions in industrial wastewater and natural water bodies. Albeit of the high sensitivity to NO3−, the electron-deficient copper sites (Cuδ+) were unstable under the negative working potentials for detection (Cuδ+ was readily reduced to Cu0). Herein, the Schiff base was grafted on MIL-125 (Ti) via covalent binding to stabilize the Cuδ+, leading to a composite Cuδ+/Schiff base/MIL-125 (Ti) material (abbreviated as CuSM) for NO3− sensing. Moreover, the unique porous structure of CuSM can speed up the diffusion rate of NO3− from the bulk solution to the surface of the modified electrode, enhancing the sensitivity of NO3− assay. As a result, the CuSM-based sensor not only exhibited a wide linear range from 1.18 µM to 58.8 mM and a low detection limit (S/N = 3) of 0.253 µM but also possesses high specificity, excellent reproducibility (the RSD of the five inter-batch sensors was 1.138%) and the ability to detect real water samples.

Regular perovskite SrTiO3 and monoclinic layered perovskite Nd2Ti2O7 for oxidative coupling of methane: Elucidating the role of chemisorbed oxygen species and lattice oxygen

Herein, regular perovskite SrTiO3 and monoclinic layered perovskite Nd2Ti2O7 have been prepared by the sol-gel method and calcined at different temperatures. As the calcination temperature of SrTiO3 increases, the Ti element on their surface is enriched, and the amount of Sr element that provides basic sites is reduced, resulting in a decrease in the number of basic sites on the catalyst surface. For Nd2Ti2O7, its surface is enriched with Nd elements, but the enrichment amount does not change with the increase in calcination temperature, and it contains less surface basic sites less than SrTiO3. Although the enrichment of Ti on the surface of SrTiO3 is conducive to the formation of oxygen vacancies, the oxygen vacancies on the surface of Nd2Ti2O7 are more abundant than those on SrTiO3. The amount of electron-deficient oxygen species on their surfaces is influenced by the presence of basic sites, which make it more favorable to stabilize electrophilic oxygen species. The C2 selective oxygen species are chemisorbed oxygen (O2-, O2δ-, O22-) for SrTiO3 and surface lattice oxygen for Nd2Ti2O7. This is because the [TiO6] octahedra in the crystal structure of SrTiO3 are tightly stacked, whereas the [TiO6] units in the Nd2Ti2O7 structure are loosely stacked, resulting in a weaker Ti-O bond strength in Nd2Ti2O7 compared with SrTiO3. In addition, the lattice oxygen of SrTiO3 has strong basicity, which is beneficial for activating gas-phase oxygen to generate chemisorbed oxygen species and stabilizing them on the catalyst surface, while the nucleophilic lattice oxygen is more likely to cause deep oxidation of methane and coupling products. However, the and basicity of lattice oxygen in Nd2Ti2O7 are weaker than those in SrTiO3, making it more favorable for C2 selectivity.

Selective Arylation of RNA 2'-OH Groups via SNAr Reaction with Trialkylammonium Heterocycles.

Small-molecule reactions at the 2'-OH groups of RNA enable useful applications for transcriptome technology and biology. To date, all reactions have involved carbonyl acylation and mechanistically related sulfonylation, limiting the types of modifications and properties that can be achieved. Here we report that electron-deficient heteroaryl species selectively react with 2'-OH groups of RNA in water via SNAr chemistry. In particular, trialkyl-ammonium (TAA)-activated aromatic heterocycles, prepared in one step from aryl chloride precursors, give high conversions to aryl ether adducts with RNAs in aqueous buffer in ~2-3 h. Remarkably, a TAA triazine previously used only for reaction with carboxylic acids, shows unprecedented selectivity for RNA over water, reacting rapidly with 2'-OH groups while exhibiting a half-life in water of >10 days. We further show that a triazine aryl species can be used as a probe at trace-level yields to map RNA structure in vitro. Finally, we prepare a number of functionalized trialkylammonium triazine reagents and show that they can be used to covalently label RNA efficiently for use in vitro and in living cells. This direct arylation chemistry offers a simple and distinct structural scaffold for post-synthetic RNA modification, with potential utility in multiple applications in transcriptome research.

Electronic structure and microenvironment modulation of Pd@UiO-66 enhances direct CO esterification to dimethyl carbonate

While the microenvironment around metal catalytic sites is recognized to be crucial in heterogeneous catalysis, its roles in CO esterification to dimethyl carbonate remain subtle. Herein, Pd nanoparticles are confined into the metal–organic frameworks with TiIV metal substitutions and functional linker groups, namely Pd@Ti-Zr-UiO-66-X (X = H, NH2, NO2). The partial substitution of metal nodes by Ti species can dramatically enhance the activity of CO, and synergistically improves catalytic performance with electron-withdrawing functionalized nitroxide linkers. As a result, Pd@Ti-Zr-UiO-66-NO2 exhibits superior conversion of CO (67.5%), selectivity for DMC (83.5%, based on all products) and WTY for DMC (1725 g·kgcat−1·h−1) much higher than those of Pd@Zr-UiO-66-H with conversion of CO (46.4%), selectivity for DMC (87%) and WTY for DMC (1175 g·kgcat−1·h−1). Based on results of experimental and DFT calculation, the synergistic effect of highly electronegative Ti species and nitro-functional linker groups with electron-withdrawing ability realizes the precise control of the electronic structure and microenvironment of Pd NPs. The number of charges transferred from Pd NPs to Zr-UiO-66 and Ti-Zr-UiO-66-NO2 increased from 1.83 to 2.69 e, respectively. The microenvironment of electron-deficient palladium species and Ti-Zr-UiO-66-NO2 promotes the activation of MN and CO, which exhibits a superior performance in direct CO esterification to dimethyl carbonate. This study not only provides a new approach for rational modulation of the chemical microenvironment of metal centers and optimization of catalytic performance but also offers important insights for the design of heterogeneous catalysts.

Sulfur doping-induced morphological and electronic structure modification of polyoxometalate FeWO4 for enhanced removal of organic pollutants from water

Wolframite (FeWO4), a typical polyoxometalate, serves as an auspicious candidate for heterogeneous catalysts, courtesy of its high chemical stability and electronic properties. However, the electron-deficient surface-active Fe species in FeWO4 are insufficient to cleave H2O2 via Fe redox-mediated Fenton-like catalytic reaction. Herein, we doped Sulfur (S) atom into FeWO4 catalysts to refine the electronic structure of FeWO4 for H2O2 activation and sulfamethoxazole (SMX) degradation. Furthermore, spin-state reconstruction on S-doped FeWO4 was found to effectively refine the electronic structure of Fe in the d orbital, thereby enhancing H2O2 activation. S doping also accelerated electron transfer during the conversion of sulfur species, promoting the cycling of Fe(III) to Fe(II). Consequently, S-doped FeWO4 bolstered the Fenton-like reaction by nearly two orders of magnitude compared to FeWO4. Significantly, the developed S-doped FeWO4 exhibited a remarkable removal efficiency of approximately 100% for SMX within 40 min in real water samples. This underscores its extensive pH adaptability, robust catalytic stability, and leaching resistance. The matrix effects of water constituents on the performance of S-doped FeWO4 were also investigated, and the results showed that a certain amount of Cl−, SO42−, NO3−, HCO3− and PO43− exhibited negligible effects on the degradation of SMX. Theoretical calculations corroborate that the distinctive spin-state reconstruction of Fe center in S-doped FeWO4 is advantageous for H2O2 decomposition. This discovery offers novel mechanistic insight into the enhanced catalytic activity of S doping in Fenton-like reactions and paves the way for expanding the application of FeWO4 in wastewater treatment.

The Electron-Rich and Nucleophilic N-Heterocyclic Imines on Metal Surfaces: Binding Modes and Interfacial Charge Transfer.

The strongly electron-donating N-heterocyclic imines (NHIs) have been employed as excellent surface anchors for the thermodynamic stabilization of electron-deficient species due to their enhanced nucleophilicity. However, the binding mode and interfacial property of these new ligands are still unclear, representing a bottleneck for advanced applications in surface functionalization and catalysis. Here, NHIs with different side groups have been rationally designed, synthesized, and analyzed on various metal surfaces (Cu, Ag). Our results reveal different binding modes depending on the molecular structure and metal surface. The molecular design enables us to achieve a flat-lying or upright configuration and even a transition between these two binding modes depending on the coverage and time. Importantly, the two binding modes exhibit different degrees of interfacial charge transfer between the molecule and the surface. This study provides essential microscopic insight into the NHI adsorption geometry and interfacial charge transfer for the optimization of heterogeneous catalysts in coordination chemistry.

Reliable Information about Electrochemical Potentials from Cyclic Voltammograms That Look “Messy”

The importance of voltammetry for characterizing electronic properties of molecular species and (nano)materials cannot be overstated. Among the most broadly used electroanalytical techniques, cyclic voltammetry (CV) offers an incomparably facile means for estimating standard electrochemical potentials, E (0), which are essential for analysis of charge transfer, energy conversion and photocatalysis [Phys. Chem. Chem. Phys. 2020, 22, 21583-21629]. Redox irreversibility, liquid-junction potentials, and uncertainties about the microenvironment on the surfaces of polarized working electrodes present key challenges for the validity of CV analysis [Curr. Opin. Electrochem. 2022, 31, 100862]. As an average of anodic and cathodic peak potentials extracted from cyclic voltammograms, half-wave potentials, E (1/2), serve as a good approximation for E (0). This approximation is acceptable for results from voltammograms exhibiting even partial chemical reversibility [J. Electrochem. Soc. 2019, 166, H3175-H3187]. Conversely, cyclic voltammograms lacking an anodic or cathodic peak die to irreversible reduction or oxidation, respectively, render estimating E (1/2) impossible. In fact, irreversibility of electrochemical oxidation and reduction is more or less the rule rather than the exception. Statistical analysis of a series of voltammograms allows us to demonstrate that the potentials at the inflection points at the rise of the cathodic and anodic waves represent a good approximation of E (1/2) for reduction and oxidation, respectively [J. Electrochem. Soc. 2019, 166, H3175-H3187]. The use of inflection potentials significantly broadens the applicability of CV for extracting meaningful results from voltammograms showing irreversible behavior. It allows us to investigate in parallel a series of electron-rich and electron-deficient polycyclic aromatic species not only with similar structures, but also with similar spin-density distributions of their radical ions, regardless their stability and reversible redox behavior in different solution media. Reformulating the Rehm-Weller equation for CT thermodynamic analysis, offers a means for eliminating the effects of liquid-junction potentials while studying electron donor-acceptor pairs [Proc. Natl. Acad. Sci. USA 2021, 118, e2026462118]. Employing this approach to donors and acceptors with similar structures reveals patterns correlated with the microenvironment at the surfaces of polarized working electrodes. Global-fit analysis of the dependence of CV-extracted reduction potentials on the concentration of the supporting electrolyte for different solvents yields information about the liquid-junction potentials in the electrochemical cell and about the polarity of the microenvironment of the redox species at the electrode surface [J. Phys. Chem. B 2023, 127, 1443-1458]. These outcomes offer a key foundation not only for improved voltammetric estimates of standard electrochemical potentials of redox species, but also for the polarity dependence of these potentials, permitting their broad applicability to systems in widely different media.

Reductive amination of 1,6-hexanediol with a modified Ru/Al2O3 catalyst

The synthesis of 1,6–hexamethylenediamine via the reductive amination of 1,6–hexanediol is a fascinating green process and a challenging topic. We developed a kind of Ru/PRL(x)–Al2O3 catalyst for the reductive amination of 1,6–hexanediol, the active Ru species was highly dispersed and anchored by the CNx species formed from 1,10-phenanthroline (PRL). The Ru particle dispersion, electronic interaction, and acid–basic property as well as the catalytic mechanism and the rate determining step were discussed in detail. The new and more acid–base pairs formed, and the electron deficient Ru species and smaller nanoparticles are responsible for the improved catalytic performances of Ru/PRL–Al2O3 catalyst. The yield of 1,6–hexamethylenediamine could reach to 54%, which is the best results reported up to now. The present catalytic process is of great potential for industrial application as it is a green process compared to the traditional method for 1,6–hexamethylenediamine production.

Synthesis and Characterization of Novel Thienothiadiazole-Based D-π-A-π-D Fluorophores as Potential NIR Imaging Agents.

As fluorescence bioimaging has increased in popularity, there have been numerous reports on designing organic fluorophores with desirable properties amenable to perform this task, specifically fluorophores with emission in the near-infrared II (NIR-II) region. One such strategy is to utilize the donor-π-acceptor-π-donor approach (D-π-A-π-D), as this allows for control of the photophysical properties of the resulting fluorophores through modulation of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels. Herein, we illustrate the properties of thienothiadiazole (TTD) as an effective acceptor moiety in the design of NIR emissive fluorophores. TTD is a well-known electron-deficient species, but its use as an acceptor in D-π-A-π-D systems has not been extensively studied. We employed TTD as an acceptor unit in a series of two fluorophores and characterized the photophysical properties through experimental and computational studies. Both fluorophores exhibited emission maxima in the NIR-I that extends into the NIR-II. We also utilized electron paramagnetic resonance (EPR) spectroscopy to rationalize differences in the measured quantum yield values and demonstrated, to our knowledge, the first experimental evidence of radical species on a TTD-based small-molecule fluorophore. Encapsulation of the fluorophores using a surfactant formed polymeric nanoparticles, which were studied by photophysical and morphological techniques. The results of this work illustrate the potential of TTD as an acceptor in the design of NIR-II emissive fluorophores for fluorescence bioimaging applications.

Direct C(3)5-H Polyfluoroarylation of 2-Amino/alkoxy Pyridines Enabled by a Transient and Electron-deficient Palladium Intermediate.

Herein, we present an unprecedented azine-limited C5-H polyfluoroarylation of 2-aminopyridines enabled by a transient and electron-deficient perfluoroaryl-Pd species via C-H/C-H coupling. The protocol further allows C3(5)-H polyfluoroarylation of 2-alkoxypyridines guided by sterics and electronics for the first time. The late-stage C-H functionalization of drugs, drug derivatives, and natural product derivatives and synthesis of C5-aryl drug derivatives further demonstrated the method's utility. The preliminary mechanistic studies reveal that the synergistic combination of the bulky yet electrophilic perfluoroaryl-Pd species and the partial nucleophilicity of the C5-position of 2-amino/alkoxy-pyridines is the origin of reactivity and selectivity. Importantly, the first experimental evidence for the role of diisopropyl sulfide is provided.

Modulating Pt nanoparticles confined in UiO-66 by linker functional groups for controllable hydrogenation

Encapsulation of clean metal nanoparticles (NPs) into interior of metal–organic framework (MOF) is of great importance to remarkably improve the stability and tune the catalytic performance of metal NPs. Herein, highly dispersed Pt NPs are encapsulated in UiO-66 with different functional groups on linker (UiO-66-X, X = F, H, NH2, OH) through enhanced electron attraction of metal precursor by MOF node and proper reduction by H2/Ar gas. Compared with traditional impregnation method, the encapsulation method gives well-defined Pt NPs and controllable microenvironment. Detailed characterizations reveal that functional group of the linker can effectively tune the microenvironment and electronic properties of guest Pt NPs. In situ FTIR was utilized to investigate the adsorption capability and strength of reactants on the catalysts. The electron-deficient Pt species and appropriate surface hydrophobicity match well with the reactants, which is responsible for enhanced catalytic hydrogenation activity of CC and nitro groups. The surface hydrophobicity plays a major role in promoting alkyne hydrogenation. This work is devoted to rationalize the relationship between hydrogenation performance and catalyst property of UiO-66 encapsulated Pt NPs, in terms of energy adaptability in electronic state and structure adaptability in surface chemistry. Rational design strategy of Pt-confined-in-MOF composites through molecular level regulation is provided for hydrogenation.

Structural Evolution of Iron-Loaded Metal-Organic Framework Catalysts for Continuous Gas-Phase Oxidation of Methane to Methanol.

Catalytic partial oxidation of methane presents a promising route to convert the abundant but environmentally undesired methane gas to liquid methanol with applications as an energy carrier and a platform chemical. However, an outstanding challenge for this process remains in developing a catalyst that can oxidize methane selectively to methanol with good activity under continuous flow conditions in the gas phase using O2 as an oxidant. Here, we report a Fe catalyst supported by a metal-organic framework (MOF), Fe/UiO-66, for the selective and on-stream partial oxidation of methane to methanol. Kinetic studies indicate the continuous production of methanol at a superior reaction rate of 5.9 × 10-2 μmolMeOH gFe-1 s-1 at 180 °C and high selectivity toward methanol, with the catalytic turnover verified by transient methane isotopic measurements. Through an array of spectroscopic characterizations, electron-deficient Fe species rendered by the MOF support is identified as the probable active site for the reaction.

Experimental Evidence for Alloying Effects in Au–Pt-Catalyzed Low-Temperature CH4Activation with NO

The activation of methane with nitric oxide at low temperatures (300–400 °C) and atmospheric pressure was studied on Au–Pt nanoparticles with different Au/Pt ratios supported on alumina. The reaction forms HCN, a valuable chemical intermediate, via concurrent or successive C–H bond cleavage, NO dissociation, and C–N coupling reactions. The catalysts with different Au/Pt ratios had similar particle morphology and bulk properties, as evidenced by scanning transmission electron microscopy imaging and X-ray absorption near-edge structure spectroscopy, respectively. However, they exhibited different electronic and geometric surface properties, according to in situ diffuse reflectance infrared Fourier transform spectra of preadsorbed CO, a likely consequence of Au surface enrichment. These differences had catalytic implications, where the relative proportion of electron-deficient Pt sites on the surface of the catalysts was found to track with activity, expressed as turnover frequency for the total CH4 conversion and HCN formation. Based on the activity trend, kinetic comparison of reaction orders, temperature-programmed desorption experiments, and comparisons to the literature, it is proposed that the CH4–NO catalysis occurred mainly on contiguous Pt sites, that the higher C–H activation activity of electron-deficient Pt species may be related to weaker adsorption of CH4, and that the higher NO dissociation activity of metallic Pt species may have contributed to the complete oxidation of CH4 to CO2. Nonetheless, contact time and in situ spectroscopic studies at isothermal conditions revealed only subtle differences in the reaction scheme by surface modifications, indicating that Au affected the reactivity indirectly.

The optimized Fenton-like activity of Fe single-atom sites by Fe atomic clusters–mediated electronic configuration modulation

The performance optimization of isolated atomically dispersed metal active sites is critical but challenging. Here, TiO2@Fe species-N-C catalysts with Fe atomic clusters (ACs) and satellite Fe-N4 active sites were fabricated to initiate peroxymonosulfate (PMS) oxidation reaction. The AC-induced charge redistribution of single atoms (SAs) was verified, thus strengthening the interaction between SAs and PMS. In detail, the incorporation of ACs optimized the HSO5- oxidation and SO5·-desorption steps, accelerating the reaction progress. As a result, the Vis/TiFeAS/PMS system rapidly eliminated 90.81% of 45 mg/L tetracycline (TC) in 10 min. The reaction process characterization suggested that PMS as an electron donor would transfer electron to Fe species in TiFeAS, generating 1O2. Subsequently, the hVB+ can induce the generation of electron-deficient Fe species, promoting the reaction circulation. This work provides a strategy to construct catalysts with multiple atom assembly-enabled composite active sites for high-efficiency PMS-based advanced oxidation processes (AOPs).

Realizing and Revealing Complex Isobutyl Alcohol Production over a Simple Cu–ZrO2 Catalyst

CO hydrogenation to isobutyl alcohol is a promising route for CO transformation to high value-added products. However, the formation mechanism of isobutyl alcohol is complex, and its synthesis requires complex catalysts and harsh reaction conditions, which hinders the identification of active sites. Herein, we efficiently synthesized isobutyl alcohol under mild conditions over a simple Cu–ZrO2 catalyst by decreasing the Cu loading. The space–time yield (STY) of isobutyl alcohol using an optimal CZ-0.11 catalyst was as high as 61.3 g·Lcat–1·h–1 with a CO conversion of 19.2%, far surpassing the STY of the state-of-the-art isobutyl alcohol synthesis (44.6 g·Lcat–1·h–1) under harsh conditions. Decreasing the Cu loading increased the distribution of smaller Cu particles and clarified the structure–activity relationship of Cu–Zr interactions for isobutyl alcohol synthesis. The enhanced Cu–Zr interaction led to the formation of more electron-deficient Cu species on the CZ-0.11 catalyst, which enriched the linearly adsorbed CO on Cu, as demonstrated by in situ diffuse reflectance infrared Fourier-transform spectroscopy. Experimental and theoretical results revealed that coupling of the bicarbonate species on ZrO2 with the linearly adsorbed CO species on electron-deficient Cu clusters promoted the formation of C2 intermediates and finally produced isobutyl alcohol through rapid β-addition. These insights into the active sites for CO hydrogenation to isobutyl alcohol may guide further catalyst designs.