A Universal Synthesis of Single-Atom Catalysts via Operando Bond Formation Driven by Electricity.

Single-atom catalysts (SACs), featuring highly uniform active sites, tunable coordination environments, and synergistic effects with support, have emerged as one of the most efficient catalysts for various reactions, particularly for electrochemical CO2 reduction (ECR). However, the scalability of SACs is restricted due to the limited choice of available support and problems that emerge when preparing SACs by thermal deposition. Here, an in situ reconstruction method for preparing SACs is developed with a variety of atomic sites, including nickel, cadmium, cobalt, and magnesium. Driven by electricity, different oxygen-containing metal precursors, such as MOF-74 and metal oxides, are directly atomized onto nitrogen-doped carbon (NC) supports, yielding SACs with variable metal active sites and coordination structures. The electrochemical force facilitates the in situ generation of bonds between the metal and the supports without the need for additional complex steps. A series of MNxOy (M denotes metal) SACs on NC have been synthesized and utilized for ECR. Among these, NiNxOy SACs using Ni-MOF-74 as a metal precursor exhibit excellent ECR performance. This universal and general SAC synthesis strategy at room temperature is simpler than most reported synthesis methods to date, providing practical guidance for the design of the next generation of high-performance SACs.

Active nitrogen sites on nitrogen doped carbon for highly efficient associative ammonia decomposition.

Nitrogen doped carbon materials have been studied as catalyst support for ammonia decomposition. There are 4 different types of nitrogen environments (graphitic, pyrrolic, pyridinic and nitrogen oxide) on the amorphous support identified. In this paper, we report a 5%Ru on MgCO3 pre-treated nitrogen doped carbon catalyst with high content of edge nitrogen-containing sites which displays an ammonia conversion rate of over 90% at 500°C and WHSV = 30,000 mL gcat -1 h-1. It also gives an impressive hydrogen production rate of 31.3 mmol/(min gcat) with low apparent activation energy of 43 kJ mol-1. Fundamental studies indicate that the distinct average Ru-N4 coordination site on edge regions is responsible for such high catalytic activity. Ammonia is stepwise decomposed via a Ru-N(H)-N(H)-Ru intermediate. This associative mechanism circumvents the direct cleavage of energetic surface nitrogen from metal to form N2 hence lowering the activation barrier for the decomposition over this catalyst.

High-Stable All-Iron Redox Flow Battery with Innovative Anolyte based on Steric Hindrance Regulation.

All-soluble all-iron redox flow batteries (AIRFBs) are an innovative energy storage technology that offer significant financial benefits. Stable and affordable redox-active materials are essential for the commercialization of AIRFBs, yet the battery stability must be significantly improved to achieve practical value. Herein, ferrous complexes combined with the triisopropanolamine (TIPA) ligand are identified as promising anolytes to extend battery life by reducing cross-contamination due to a pronounced steric hindrance effect. The coordination structure and failure mechanism of our Fe-TIPA complexes were determined by molecular dynamics simulation and spectroscopic experiments. By coupling with [Fe(CN)6]4-/3-, Fe-TIPA/Fe-CN AIRFBs retained excellent stability exceeding 1831 cycles at 80 mA ⋅ cm-2, yielding an energy efficiency of ~80 % and maintaining a steady discharge capacity. Moreover, the all-soluble electrolyte was tested in an industrial-scale Fe-TIPA/Fe-CN AIRFB prototype energy storage system, where an energy efficiency of 81.3 % was attained. Given the abundance of iron resources, we model the TIPA AIRFB electrolyte cost to be as low as 32.37 $/kWh, which is significantly cheaper than the current commercial level. This work demonstrates that steric hindrance is an effective measure to extended battery life, facilitating the commercial development of affordable flow batteries.

Stabilization of Ni-containing Keggin-type polyoxometalates with variable oxidation states as novel catalysts for electrochemical water oxidation.

The development of new recyclable and inexpensive electrochemically active species for water oxidation catalysis is the most crucial step for future utilization of renewables. Particularly, transition metal complexes containing internal multiple, cooperative metal centers to couple with redox catalysts in the inorganic Keggin-type polyoxometalate (POM) framework at high potential or under extreme pH conditions would be promising candidates. However, most reported Ni-containing POMs have been highly unstable towards hydrolytic decomposition, which precludes them from application as water oxidation catalysts (WOCs). Here, we have prepared new tri-Ni-containing POMs with variable oxidation states by charge tailored synthetic strategies for the first time and developed them as recyclable POMs for water oxidation catalysts. In addition, by implanting corresponding POM anions into the positively charged MIL-101(Cr) metal-organic framework (MOF), the entrapped Ni2+/Ni3+ species can show complete recyclability for water oxidation catalysis without encountering uncontrolled hydrolysis of the POM framework. As a result, a low onset potential of approximately 1.46 V vs. NHE for water oxidation with stable WOC performance is recorded. Based on this study, rational design and stabilization of other POM-electrocatalysts containing different multiple transition metal centres could be made possible.

Facet-Dependent Surface Restructuring on Nickel (Oxy)hydroxides: A Self-Activation Process for Enhanced Oxygen Evolution Reaction.

Unraveling the catalyst surface structure and behavior during reactions is essential for both mechanistic understanding and performance optimization. Here we report a phenomenon of facet-dependent surface restructuring intrinsic to ß-Ni(OH)2 catalysts during oxygen evolution reaction (OER), discovered by the correlative ex situ and operando characterization. The ex situ study after OER reveals ß-Ni(OH)2 restructuring at the edge facets to form nanoporous Ni1-xO, which is Ni deficient containing Ni3+ species. Operando liquid transmission electron microscopy (TEM) and Raman spectroscopy further identify the active role of the intermediate ß-NiOOH phase in both the OER catalysis and Ni1-xO formation, pinpointing the complete surface restructuring pathway. Such surface restructuring is shown to effectively increase the exposed active sites, accelerate Ni oxidation kinetics, and optimize *OH intermediate bonding energy toward fast OER kinetics, which leads to an extraordinary activity enhancement of ∼16-fold. Facilitated by such a self-activation process, the specially prepared ß-Ni(OH)2 with larger edge facets exhibits a 470-fold current enhancement than that of the benchmark IrO2, demonstrating a promising way to optimize metal-(oxy)hydroxide-based catalysts.

Synthesis of core@shell catalysts guided by Tammann temperature.

Designing high-performance thermal catalysts with stable catalytic sites is an important challenge. Conventional wisdom holds that strong metal-support interactions can benefit the catalyst performance, but there is a knowledge gap in generalizing this effect across different metals. Here, we have successfully developed a generalizable strong metal-support interaction strategy guided by Tammann temperatures of materials, enabling functional oxide encapsulation of transition metal nanocatalysts. As an illustrative example, Co@BaAl2O4 core@shell is synthesized and tracked in real-time through in-situ microscopy and spectroscopy, revealing an unconventional strong metal-support interaction encapsulation mechanism. Notably, Co@BaAl2O4 exhibits exceptional activity relative to previously reported core@shell catalysts, displaying excellent long-term stability during high-temperature chemical reactions and overcoming the durability and reusability limitations of conventional supported catalysts. This pioneering design and widely applicable approach has been validated to guide the encapsulation of various transition metal nanoparticles for environmental tolerance functionalities, offering great potential to advance energy, catalysis, and environmental fields.

Investigation of dynamical X-ray back diffraction at grazing incidence.

We report a theoretical investigation of X-ray back diffraction at grazing incidence. Based on the framework of the dynamical theory of X-ray diffraction, the grazing incidence for Si (12 4 0) back diffraction is taken as an example to resolve the eigenvalue problem inside the crystal. The dispersion surface and the resulting diffraction intensities are strongly affected by the miscut angle as well as the diffraction geometry of grazing incidence. The kinematical relationship between the incident angle and the miscut angle is well explained by Snell's law. While only the two-beam diffraction is considered, our treatment can be further extended to include the cases for multiple diffractions as well.

Hollow-Carbon Confinement Annealing: A New Synthetic Approach to Make High-Entropy Solid-Solution and Intermetallic Nanoparticles.

High-entropy alloy (HEA) nanoparticles (NPs) have been emerging with superior compositional tunability and multielemental synergy, presenting a unique platform for material discovery and performance optimization. Here we report a synthetic approach utilizing hollow-carbon confinement in the ordinary furnace annealing to achieve the nonequilibrium HEA-NPs such as Pt0.45Fe0.18Co0.12Ni0.15Mn0.10 with uniform size ∼5.9 nm. The facile temperature control allows us not only to reveal the detailed reaction pathway through ex situ characterization but also to tailor the HEA-NP structure from the crystalline solid solution to intermetallic. The preconfinement of metal precursors is the key to ensure the uniform distribution of metal nanoparticles with confined volume, which is essential to prevent the thermodynamically favored phase separation even during the ordinary furnace annealing. Besides, the synthesized HEA-NPs exhibit remarkable activity and stability in oxygen reduction catalysis. The demonstrated synthetic approach may significantly expand the scope of HEA-NPs with uncharted composition and performance.

Highly defective graphene quantum dots-doped 1T/2H-MoS2 as an efficient composite catalyst for the hydrogen evolution reaction.

We present a new composite catalyst system of highly defective graphene quantum dots (HDGQDs)-doped 1T/2H-MoS2 for efficient hydrogen evolution reactions (HER). The high electrocatalytic activity, represented by an overpotential of 136.9 mV and a Tafel slope of 57.1 mV/decade, is due to improved conductivity, a larger number of active sites in 1T-MoS2 compared to that in 2H-MoS2, and additional defects introduced by HDGQDs. High-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) were used to characterize both the 1T/2H-MoS2 and GQDs components while Fourier-transform infrared spectroscopy (FTIR) was employed to identify the functional groups on the edge and defect sites in the HDGQDs. The morphology of the composite catalyst was also examined by field emission scanning electron microscopy (FESEM). All experimental data demonstrated that each component contributes unique advantages that synergistically lead to the significantly improved electrocatalytic activity for HER in the composite catalyst system.

Photo-Induced Active Lewis Acid-Base Pairs in a Metal-Organic Framework for H2 Activation.

The establishment of active sites as the frustrated Lewis pair (FLP) has recently attracted much attention ranging from homogeneous to heterogeneous systems in the field of catalysis. Their unquenched reactivity of Lewis acid and base pairs in close proximity that are unable to form stable adducts has been shown to activate small molecules such as dihydrogen heterolytically. Herein, we show that grafted Ru metal-organic framework-based catalysts prepared via N-containing linkers are rather catalytically inactive for H2 activation despite the application of elevated temperatures. However, upon light illumination, charge polarization of the anchored Ru bipyridine complex can form a transient Lewis acid-base pair, Ru+-N- via metal-to-ligand charge transfer, as confirmed by time-dependent density functional theory (TDDFT) calculations to carry out effective H2-D2 exchange. FTIR and 2-D NMR endorse the formation of such reactive intermediate(s) upon light irradiation.

General Strategy toward Hydrophilic Single Atom Catalysts for Efficient Selective Hydrogenation.

Well dispersible and stable single atom catalysts (SACs) with hydrophilic features are highly desirable for selective hydrogenation reactions in hydrophilic solvents towards important chemicals and pharmaceutical intermediates. A general strategy is reported for the fabrication of hydrophilic SACs by cation-exchange approach. The cation-exchange between metal ions (M = Ni, Fe, Co, Cu) and Na+ ions introduced in the skeleton of metal oxide (TiO2 or ZrO2 ) nanoshells plays the key role in forming M1 /TiO2 and M1 /ZrO2 SACs, which efficiently prevents the aggregation of the exchanged metal ions. The as-obtained SACs are highly dispersible and stable in hydrophilic solvents including alcohol and water, which greatly facilitates the catalysis reaction in alcohol. The Ni1 /TiO2 SACs have been successfully utilized as catalysts for the selective C=C hydrogenation of cinnamaldehyde to produce phenylpropanal with 98% conversion, over 90% selectivity, good recyclability, and a turnover frequency (TOF) of 102 h-1 , overwhelming most reported catalysts including noble metal catalysts.

Single-Atom Molybdenum-N3 Sites for Selective Hydrogenation of CO2 to CO.

The design of efficient non-noble metal catalysts for CO2 hydrogenation to fuels and chemicals is desired yet remains a challenge. Herein, we report that single Mo atoms with a MoN3 (pyrrolic) moiety enable remarkable CO2 adsorption and hydrogenation to CO, as predicted by density functional theory studies and evidenced by a high and stable conversion of CO2 reaching about 30.4 % with a CO selectivity of almost 100 % at 500 °C and very low H2 partial pressure. Atomically dispersed MoN3 is calculated to facilitate CO2 activation and reduces CO2 to CO* via the direct dissociation path. Furthermore, the highest transition state energy in CO formation is 0.82 eV, which is substantially lower than that of CH4 formation (2.16 eV) and accounts for the dominant yield of CO. The enhanced catalytic performances of Mo/NC originate from facile CO desorption with the help of dispersed Mo on nitrogen-doped carbon (Mo/NC), and in the absence of Mo nanoparticles. The resulting catalyst preserves good stability without degradation of CO2 conversion rate even after 68 hours of continuous reaction. This finding provides a promising route for the construction of highly active, selective, and robust single-atom non-precious metal catalysts for reverse water-gas shift reaction.

Formation of Co-O bonds and reversal of thermal annealing effects induced by X-ray irradiation in (Y, Co)-codoped CeO2 nanocrystals.

We report an unconventional effect of synchrotron X-ray irradiation in which Co-O bonds in thermally annealed (Y, Co)-codoped CeO2 nanocrystal samples were formed due to, instead of broken by, X-ray irradiation. Our experimental data indicate that escaping oxygen atoms from X-ray-broken Ce-O bonds may be captured by Co dopant atoms to form additional Co-O bonds. Consequently, the Co dopant atoms were pumped by X-rays from the energetically-favored thermally-stable Co-O4 square-planar structure to the metastable octahedral Co-O6 environment, practically a reversal of thermal annealing effects in (Y, Co)-codoped CeO2 nanocrystals. The band gap of doped CeO2 with Co dopant in the Co-O6 structure was previously found to be 1.61 eV higher than that with Co in the Co-O4 environment. Therefore, X-ray irradiation can work with thermal annealing in opposing directions to fine tune and optimize the band gap of the material for specific technological applications.

Extraction method development for nanoplastics from oyster and fish tissues.

Nanoplastics are now found in some environmental media and consumer products. However, very limited data on nanoplastics are available for one of the main human consumption sources of microplastics: seafood. Unlike microplastics, a method for extracting nanoplastics from seafood is still lacking. Herein, a combination of common extraction techniques including enzymatic digestion, sequential membrane filtration, centrifugal concentration, and purification (dialysis and sodium dodecylsulfate (SDS) incubation), was developed to extract nanoplastics from oyster and fish tissues. Corolase with subsequent lipase treatment achieved the highest digestion efficiencies (88- 89%) for non-homogenized tissues compared to other proteases and additional cellulase or H2O2 treatment. With the exception of polyethylene terephthalate (PET), enzymatic digestion did not change the morphology or structure of polyvinyl chloride (PVC), polyethylene (PE), or polystyrene (PS) nanoplastic particles, and the subsequent extraction procedures had good recoveries of 71- 110% for fluorescence-labeled 76-nm PVC and 100- and 750-nm PS, as validated by a Nanoparticle Tracking Analysis (NTA). Few of the 1011 digested residual particles of 150- 300 nm in diameter per oyster or per serving of fish tissue were left in the method blank. Consequently, this efficient approach could be used as a pretreatment protocol for current potential nanoplastic detection methods.

High Loading of Transition Metal Single Atoms on Chalcogenide Catalysts.

Transition metal doped chalcogenides are one of the most important classes of catalysts that have been attracting increasing attention for petrochemical and energy related chemical transformations due to their unique physiochemical properties. For practical applications, achieving maximum atom utilization by homogeneous dispersion of metals on the surface of chalcogenides is essential. Herein, we report a detailed study of a deposition method using thiourea coordinated transition metal complexes. This method allows the preparation of a library of a wide range of single atoms including both noble and non-noble transition metals (Fe, Co, Ni, Cu, Pt, Pd, Ru) with a metal loading as high as 10 wt % on various ultrathin 2D chalcogenides (MoS2, MoSe2, WS2 and WSe2). As demonstrated by the state-of-the-art characterization, the doped single transition metal atoms interact strongly with surface anions and anion vacancies in the exfoliated 2D materials, leading to high metal dispersion in the absence of agglomeration. Taking Fe on MoS2 as a benchmark, it has been found that Fe is atomically dispersed until 10 wt %, and beyond this loading, formation of coplanar Fe clusters is evident. Atomic Fe, with a high electron density at its conduction band, exhibits a superior intrinsic activity and stability in CO2 hydrogenation to CO per Fe compared to corresponding surface Fe clusters and other Fe catalysts reported for reverse water-gas-shift reactions.

Rapid Interchangeable Hydrogen, Hydride, and Proton Species at the Interface of Transition Metal Atom on Oxide Surface.

Hydrogen spillover is the phenomenon where a hydrogen atom, generated from the dissociative chemisorption of dihydrogen on the surface of a metal species, migrates from the metal to the catalytic support. This phenomenon is regarded as a promising avenue for hydrogen storage, yet the atomic mechanism for how the hydrogen atom can be transferred to the support has remained controversial for decades. As a result, the development of catalytic support for such a purpose is only limited to typical reducible oxide materials. Herein, by using a combination of in situ spectroscopic and imaging technique, we are able to visualize and observe the atomic pathway for which hydrogen travels via a frustrated Lewis pair that has been constructed on a nonreducible metal oxide. The interchangeable status between the hydrogen, proton, and hydride is carefully characterized and demonstrated. It is envisaged that this study has opened up new design criteria for hydrogen storage material.

Reduction of dopant ions and enhancement of magnetic properties by UV irradiation in Ce-doped TiO2.

We report the experimental observation of and theoretical explanation for the reduction of dopant ions and enhancement of magnetic properties in Ce-doped TiO2 diluted magnetic semiconductors from UV-light irradiation. Substantial increase in Ce3+ concentration and creation of oxygen vacancy defects in the sample due to UV-light irradiation was observed by X-ray and optical methods. Magnetic measurements demonstrate a combination of paramagnetism and ferromagnetism up to room temperatures in all samples. The magnetization of both paramagnetic and ferromagnetic components was observed to be dramatically enhanced in the irradiated sample. First-principle theoretical calculations show that valence holes created by UV irradiation can substantially lower the formation energy of oxygen vacancies. While the electron spin densities for defect states near oxygen vacancies in pure TiO2 are in antiferromagnetic orientation, they are in ferromagnetic orientations in Ce-doped TiO2. Therefore, the ferromagnetically-oriented spin densities near oxygen vacancies created by UV irradiation are the most probable cause for the experimentally observed enhancement of magnetism in the irradiated Ce-doped TiO2.

Controlled synthesis of Bi- and tri-nuclear Cu-oxo nanoclusters on metal-organic frameworks and the structure-reactivity correlations.

Precisely tuning the nuclearity of supported metal nanoclusters is pivotal for designing more superior catalytic systems, but it remains practically challenging. By utilising the chemical and molecular specificity of UiO-66-NH2 (a Zr-based metal-organic framework), we report the controlled synthesis of supported bi- and trinuclear Cu-oxo nanoclusters on the Zr6O4 nodal centres of UiO-66-NH2. We revealed the interplay between the surface structures of the active sites, adsorption configurations, catalytic reactivities and associated reaction energetics of structurally related Cu-based 'single atoms' and bi- and trinuclear species over our model photocatalytic formic acid reforming reaction. This work will offer practical insight that fills the critical knowledge gap in the design and engineering of new-generation atomic and nanocluster catalysts. The precise control of the structure and surface sensitivities is important as it can effectively lead to more reactive and selective catalytic systems. The supported bi- and trinuclear Cu-oxo nanoclusters exhibit notably different catalytic properties compared with the mononuclear 'Cu1' analogue, which provides critical insight for the engineering of more superior catalytic systems.

A rational study on the geometric and electronic properties of single-atom catalysts for enhanced catalytic performance.

We investigate the geometric and electronic properties of single-atom catalysts (SACs) within metal-organic frameworks (MOFs) with respect to electrocatalytic CO2 reduction as a model reaction. A series of mid-to-late 3d transition metals have been immobilised within the microporous cavity of UiO-66-NH2. By employing Rietveld refinement of new-generation synchrotron diffraction, we not only identified the crystallographic and atomic parameters of the SACs that are stabilised with a robust MN(MOF) bonding of ca. 2.0 Å, but also elucidated the end-on coordination geometry with CO2. A volcano trend in the FEs of CO has been observed. In particular, the confinement effect within the rigid MOF can greatly facilitate redox hopping between the Cu SACs, rendering high FEs of CH4 and C2H4 at a current density of -100 mA cm-2. Although only demonstrated in selected SACs within UiO-66-NH2, this study sheds light on the rational engineering of molecular interactions(s) with SACs for the sustainable provision of fine chemicals.