Structurally Locked High-Crystalline Covalent Triazine Frameworks Enable Remarkable Overall Photosynthesis of Hydrogen Peroxide.

The development of green and efficient hydrogen peroxide (H2O2) production is of great interest but remains challenging. Herein, we develop a new and simple strategy via locking the coplanarity in highly crystalline covalent triazine frameworks (CTFs) to remarkably boost direct photosynthesis of H2O2 from oxygen and water. The exfoliated ultrathin 2D-CTF nanosheets exhibit excellent photocatalytic H2O2 evolution with an ultrahigh solar-to-chemical efficiency of 0.91% and a superb apparent quantum yield of 16.8% at 420 nm, surpassing all previous CTFs and most of the metal-free photocatalysts ever reported. Our detailed experimental and theoretical studies reveal that the spatially locked structure in the crystalline CTF photocatalyst can not only greatly enhance the separation and transfer of photoexcited charge-carriers for promoting H2O2 photogeneration but also alter the local electronic structures that unexpectedly turn water oxidation from a four-electron route to a two-electron pathway, resulting in a 100% atom utilization efficiency. This work provides valuable insights into the designed synthesis of highly efficient metal-free photocatalysts and precise control over photocatalytic reaction pathways in organic materials.

Atomically dispersed hexavalent iridium oxide from MnO2 reduction for oxygen evolution catalysis.

Hexavalent iridium (IrVI) oxide is predicted to be more active and stable than any other iridium oxide for the oxygen evolution reaction in acid; however, its experimental realization remains challenging. In this work, we report the synthesis, characterization, and application of atomically dispersed IrVI oxide (IrVI-ado) for proton exchange membrane (PEM) water electrolysis. The IrVI-ado was synthesized by oxidatively substituting the ligands of potassium hexachloroiridate(IV) (K2IrCl6) with manganese oxide (MnO2). The mass-specific activity (1.7 × 105 amperes per gram of iridium) and turnover number (1.5 × 108) exceeded those of benchmark iridium oxides, and in situ x-ray analysis during PEM operations manifested the durability of IrVI at current densities up to 2.3 amperes per square centimeter. The high activity and stability of IrVI-ado showcase its promise as an anode material for PEM electrolysis.

Spontaneous Reconstruction of Copper Active Sites during the Alkaline CORR: Degradation and Recovery of the Performance.

Understanding the reconstruction of electrocatalysts under operational conditions is essential for studying their catalytic mechanisms and industrial applications. Herein, using spatiotemporally resolved Raman spectroscopy with CO as a probe molecule, we resolved the spontaneous reconstruction of Cu active sites during cathodic CO reduction reactions (CORRs). Quasi-in situ focused ion beam transmission electron microscopy (FIB-TEM) revealed that under prolonged electrolysis, the Cu surface can reconstruct to form nanometer-sized Cu particles with (111)/(100) facets and abundant grain boundaries, which strongly favor the formation of an inactive *CObridge binding site and deteriorate the CORR performance. A short period of anodic oxidation can efficiently remove these reconstructed nanoparticles by quick dissolution of Cu, thus providing an effective strategy to regenerate the Cu catalysts and recover their CORR performance. This study provides real-time in situ observations of Cu reconstruction and changes in the binding of key reaction intermediates, highlighting the decisive role of the local active site, rather than the macroscopic morphology, on adsorption of key reaction intermediates and thus CORR performance.

Challenging thermodynamics: combining immiscible elements in a single-phase nano-ceramic.

The Hume-Rothery rules governing solid-state miscibility limit the compositional space for new inorganic material discovery. Here, we report a non-equilibrium, one-step, and scalable flame synthesis method to overcome thermodynamic limits and incorporate immiscible elements into single phase ceramic nanoshells. Starting from prototype examples including (NiMg)O, (NiAl)Ox, and (NiZr)Ox, we then extend this method to a broad range of Ni-containing ceramic solid solutions, and finally to general binary combinations of elements. Furthermore, we report an "encapsulated exsolution" phenomenon observed upon reducing the metastable porous (Ni0.07Al0.93)Ox to create ultra-stable Ni nanoparticles embedded within the walls of porous Al2O3 nanoshells. This nanoconfined structure demonstrated high sintering resistance during 640 h of catalysis of CO2 reforming of methane, maintaining constant 96% CH4 and CO2 conversion at 800 °C and dramatically outperforming conventional catalysts. Our findings could greatly expand opportunities to develop novel inorganic energy, structural, and functional materials.

Single Atom Iridium Decorated Nickel Alloys Supported on Segregated MoO2 for Alkaline Water Electrolysis.

Hetero-interface engineering has been widely employed to develop supported multicomponent catalysts for water electrolysis, but it still remains a substantial challenge for supported single atom alloys. Herein a conductive oxide MoO2 supported Ir1 Ni single atom alloys (Ir1 Ni@MoO2 SAAs) bifunctional electrocatalysts through surface segregation coupled with galvanic replacement reaction, where the Ir atoms are atomically anchored onto the surface of Ni nanoclusters via the Ir-Ni coordination accompanied with electron transfer from Ni to Ir is reported. Benefiting from the unique structure, the Ir1 Ni@MoO2 SAAs not only exhibit low overpotential of 48.6 mV at 10 mA cm-2 and Tafel slope of 19 mV dec-1 for hydrogen evolution reaction, but also show highly efficient alkaline water oxidation with overpotential of 280 mV at 10 mA cm-2 . Their overall water electrolysis exhibits a low cell voltage of 1.52 V at 10 mA cm-2 and excellent durability. Experiments and theoretical calculations reveal that the Ir-Ni interface effectively weakens hydrogen binding energy, and decoration of the Ir single atoms boost surface reconstruction of Ni species to enhance the coverage of intermediates (OH*) and switch the potential-determining step. It is suggested that this approach opens up a promising avenue to design efficient and durable precious metal bifunctional electrocatalysts.

Reactant enrichment in hollow void of Pt NPs@MnOx nanoreactors for boosting hydrogenation performance.

In confined mesoscopic spaces, the unraveling of a catalytic mechanism with complex mass transfer and adsorption processes such as reactant enrichment is a great challenge. In this study, a hollow nanoarchitecture of MnOx-encapsulated Pt nanoparticles was designed as a nanoreactor to investigate the reactant enrichment in a mesoscopic hollow void. By employing advanced characterization techniques, we found that the reactant-enrichment behavior is derived from directional diffusion of the reactant driven through the local concentration gradient and this increased the amount of reactant. Combining experimental results with density functional theory calculations, the superior cinnamyl alcohol (COL) selectivity originates from the selective adsorption of cinnamaldehyde (CAL) and the rapid formation and desorption of COL in the MnOx shell. The superb performance of 95% CAL conversion and 95% COL selectivity is obtained at only 0.5 MPa H2 and 40 min. Our findings showcase that a rationally designed nanoreactor could boost catalytic performance in chemoselective hydrogenation, which can be of great aid and potential in various application scenarios.

CuCeOx/CuO Catalyst Derived from the Layered Double Hydroxide Precursor: Catalytic Performance in NO Reduction with CO in the Presence of Water and Oxygen.

Valencies of metal species and lattice defects, such as oxygen vacancies, play a pivotal role in metal oxide-catalyzed reactions. Herein, we report a promising synthetic strategy for preparing CuO-supported CuCeOx catalysts (CuCeOx/CuO) by calcination of a hydrotalcite precursor [Cu6Ce2(OH)16]CO3·nH2O. The structural and chemical properties of catalysts were characterized by XRD, ICP-AES, TEM, TPR, NH3-TPD, XPS, Raman spectroscopy, and N2 adsorption, which revealed that the thermal pretreatment in an oxidative atmosphere caused segregation and reconstitution processes of the precursor, resulting in a mesoporous catalyst consisting of well-dispersed CuO-supported CuCeOx clusters of 1.8-3.2 nm in size with a high population of oxygen vacancies. The as-prepared catalyst shows excellent catalytic performance in the reduction of NO by CO in the absence as well as in the presence of water and oxygen. This behavior is attributed to its high oxygen defect concentration facilitating the interplay of the redox equilibria between Cu2+ and reduced copper species (Cu+/Cu0) and (Ce4+/Ce3+). The high surface population of oxygen vacancies and in situ-generated metallic copper species have been evidenced by Raman spectroscopy and X-ray photoelectron spectroscopy. The layered double hydroxide-derived CuCeOx/CuO also showed good water tolerance and long-term stability. In situ infrared spectroscopy investigations indicated that adsorbed hyponitrite species are the main reaction intermediates of the NO conversion as also corroborated by theoretical simulations.

Deforming lanthanum trihydride for superionic conduction.

With strong reducibility and high redox potential, the hydride ion (H-) is a reactive hydrogen species and an energy carrier. Materials that conduct pure H- at ambient conditions will be enablers of advanced clean energy storage and electrochemical conversion technologies1,2. However, rare earth trihydrides, known for fast H migration, also exhibit detrimental electronic conductivity3-5. Here we show that by creating nanosized grains and defects in the lattice, the electronic conductivity of LaHx can be suppressed by more than five orders of magnitude. This transforms LaHx to a superionic conductor at -40 °C with a record high H- conductivity of 1.0 × 10-2 S cm-1 and a low diffusion barrier of 0.12 eV. A room-temperature all-solid-state hydride cell is demonstrated.

One-Step Synthesis of Light Metal Nanoparticle from Metastable Complex.

Metal nanoparticles have attracted considerable scientific and technological interest in recent years, most related explorations and reports are focused on transition and noble metals. However, the synthesis and application of light metal nanoparticles represented by Mg have not been fully exploited, limited by their ultrahigh reactivity in air and preparation in harsh conditions. In this work, a simple and effective one-step organic solvent-assisted ball-milling process is developed to synthesize Mg and Li nanoparticles, which permits the formation of MgH2 in a hydrogen atmosphere in a one-step reaction process at ambient temperature. Further studies suggest that acetone chemisorbs on defects/surfaces of Mg during ball milling leading to the formation of a metastable magnesium complex, which significantly alters the physical and chemical characteristics of Mg grains. The formation of metastable complexes provides an attractive strategy to produce light metal nanoparticles and inspires the authors to study the interaction of organic solvents with light metals.

Switchable Tuning CO2 Hydrogenation Selectivity by Encapsulation of the Rh Nanoparticles While Exposing Single Atoms.

The switch of CO2 hydrogenation selectivity from CH4 to CO over TiO2 supported Rh catalysts is accomplished via selective encapsulation of Rh nanoparticles while exposing Rh single atoms by high-temperature reduction (HTR) according to their different strong metal-support interaction (SMSI) occurrence conditions, which can be reversed by subsequent oxidation treatment.

Modulating the strong metal-support interaction of single-atom catalysts via vicinal structure decoration.

Metal-support interaction predominately determines the electronic structure of metal atoms in single-atom catalysts (SACs), largely affecting their catalytic performance. However, directly tuning the metal-support interaction in oxide supported SACs remains challenging. Here, we report a new strategy to subtly regulate the strong covalent metal-support interaction (CMSI) of Pt/CoFe2O4 SACs by a simple water soaking treatment. Detailed studies reveal that the CMSI is weakened by the bonding of H+, generated from water dissociation, onto the interface of Pt-O-Fe, resulting in reduced charge transfer from metal to support and leading to an increase of C-H bond activation in CH4 combustion by more than 50 folds. This strategy is general and can be extended to other CMSI-existed metal-supported catalysts, providing a powerful tool to modulating the catalytic performance of SACs.

Potential-Driven Restructuring of Cu Single Atoms to Nanoparticles for Boosting the Electrochemical Reduction of Nitrate to Ammonia.

Restructuring is ubiquitous in thermocatalysis and of pivotal importance to identify the real active site, yet it is less explored in electrocatalysis. Herein, by using operando X-ray absorption spectroscopy in conjunction with advanced electron microscopy, we reveal the restructuring of the as-synthesized Cu-N4 single-atom site to the nanoparticles of ∼5 nm during the electrochemical reduction of nitrate to ammonia, a green ammonia production route upon combined with the plasma-assisted oxidation of nitrogen. The reduction of Cu2+ to Cu+ and Cu0 and the subsequent aggregation of Cu0 single atoms is found to occur concurrently with the enhancement of the NH3 production rate, both of them are driven by the applied potential switching from 0.00 to -1.00 V versus RHE. The maximum production rate of ammonia reaches 4.5 mg cm-2 h-1 (12.5 molNH3 gCu-1 h-1) with a Faradaic efficiency of 84.7% at -1.00 V versus RHE, outperforming most of the other Cu catalysts reported previously. After electrolysis, the aggregated Cu nanoparticles are reversibly disintegrated into single atoms and then restored to the Cu-N4 structure upon being exposed to an ambient atmosphere, which masks the potential-induced restructuring during the reaction. The synchronous changes of the Cu0 percentage and the ammonia Faradaic efficiency with the applied potential suggests that the Cu nanoparticles are the genuine active sites for nitrate reduction to ammonia, which is corroborated with both the post-deposited Cu NP catalyst and density functional theory calculations.

Atomic Insight into the Local Structure and Microenvironment of Isolated Co-Motifs in MFI Zeolite Frameworks for Propane Dehydrogenation.

Embedding metal species into zeolite frameworks can create framework-bond metal sites in a confined microenvironment. The metals sitting in the specific T sites of zeolites and their crystalline surroundings are both committed to the interaction with the reactant, participation in the activation, and transient state achievement during the whole catalytic process. Herein, we construct isolated Co-motifs into purely siliceous MFI zeolite frameworks (Co-MFI) and reveal the location and microenvironment of the isolated Co active center in the MFI zeolite framework particularly beneficial for propane dehydrogenation (PDH). The isolated Co-motif with the distorted tetrahedral structure ({(≡SiO)2Co(HO-Si≡)2}, two Co-O-Si bonds, and two pseudobridging hydroxyls (Co···OH-Si) is located at T1(7) and T3(9) sites of the MFI zeolite. DFT calculations and deuterium-labeling reactions verify that the isolated Co-motif together with the MFI microenvironment collectively promotes the PDH reaction by providing an exclusive microenvironment to preactivate C3H8, polarizing the oxygen in Co-O-Si bonds to accept H* ({(≡SiO)CoHδ- (Hδ+O-Si≡)3}), and a scaffold structure to stabilize the C3H7* intermediate. The Co-motif active center in Co-MFI goes through the dynamic evolutions and restoration in electronic states and coordination states in a continuous and repetitive way, which meets the requirements from the series of elementary steps in the PDH catalytic cycle and fulfills the successful catalysis like enzyme catalysis.

Ultrafine PtCoRh nanorods for highly efficient hydrogen evolution reaction in acid.

PtCoRh nanorods with an average width of 1.6 ± 0.2 nm show an overpotential of 6.1 mV at 10 mA cm-2 toward acidic HER. The exceptional activity originates from a high electrochemically active surface area of 130.1 m2 gPt-1 and a unique Pt-H bond strength appropriately tuned by Co and Rh.

Photo-thermo semi-hydrogenation of acetylene on Pd1/TiO2 single-atom catalyst.

Semi-hydrogenation of acetylene in excess ethylene is a key industrial process for ethylene purification. Supported Pd catalysts have attracted most attention due to their superior intrinsic activity but often suffer from low selectivity. Pd single-atom catalysts (SACs) are promising to significantly improve the selectivity, but the activity needs to be improved and the feasible preparation of Pd SACs remains a grand challenge. Here, we report a simple strategy to construct Pd1/TiO2 SACs by selectively encapsulating the co-existed small amount of Pd nanoclusters/nanoparticles based on their different strong metal-support interaction (SMSI) occurrence conditions. In addition, photo-thermo catalysis has been applied to this process where a much-improved catalytic activity was obtained. Detailed characterization combined with DFT calculation suggests that photo-induced electrons transferred from TiO2 to the adjacent Pd atoms facilitate the activation of acetylene. This work offers an opportunity to develop highly stable Pd SACs for efficient catalytic semi-hydrogenation process.

Synthesis of Nickel Nitride-Based 1D/0D Heterostructure via a Morphology-Inherited Nitridation Strategy for Efficient Electrocatalytic Hydrogen Evolution.

The fabrication of heterostructures has inspired extensive interest in promoting the performance of solar cells or solar fuel production, but it is still challenging for nitrides to prepare structurally ordered heterostructures. Herein, one nickel nitride-based heterostructure composed of 1D Ni0.2 Mo0.8 N nanorods and 0D Ni3 N nanoparticles (denoted as NiMoN/NiN) is reported to exhibit significantly promoted hydrogen evolution reaction performance in both alkaline and neutral media. In particular, the optimal overpotential of the NiMoN/NiN sample at 10 mA cm-2 in 1 m KOH is 49 mV. The successful fabrication of 1D/0D heterostructures is mainly ascribed to morphology-inherited nitridation of 1D oxide precursor (denoted as NiMoO-NRs) in situ grown on Ni foam surface, and attributed to strong Lewis acid-base interaction that renders the Ni2+ ions emitted from the oxide precursor to well coordinate with NH3 for the formation of Ni3 N nanoparticles during the nitridation process. It is theoretically and experimentally demonstrated that the special 1D/0D heterostructure provides tandem active phases Ni0.2 Mo0.8 N and Ni3 N for synergistic promotion in lowering the activation energy of H2 O dissociation and optimizing the adsorption energy of H, respectively. This work may open a new avenue for developing highly active tandem electrocatalysts for promising renewable energy conversion.

Steering the reaction pathway of syngas-to-light olefins with coordination unsaturated sites of ZnGaOx spinel.

Significant progress has been demonstrated in the development of bifunctional oxide-zeolite catalyst concept to tackle the selectivity challenge in syngas chemistry. Despite general recognition on the importance of defect sites of metal oxides for CO/H2 activation, the actual structure and catalytic roles are far from being well understood. We demonstrate here that syngas conversion can be steered along a highly active and selective pathway towards light olefins via ketene-acetate (acetyl) intermediates by the surface with coordination unsaturated metal species, oxygen vacancies and zinc vacancies over ZnGaOx spinel-SAPO-34 composites. It gives 75.6% light-olefins selectivity and 49.5% CO conversion. By contrast, spinel-SAPO-34 containing only a small amount of oxygen vacancies and zinc vacancies gives only 14.9% light olefins selectivity at 6.6% CO conversion under the same condition. These findings reveal the importance to tailor the structure of metal oxides with coordination unsaturated metal sites/oxygen vacancies in selectivity control within the oxide-zeolite framework for syngas conversion and being anticipated also for CO2 hydrogenation.

Ni2+ -Directed Anisotropic Growth of PtCu Nested Skeleton Cubes Boosting Electroreduction of Oxygen.

Structure-controlled Pt-based nanocrystals have the great potential to provide a flexible strategy for improving the catalysis of the oxygen reduction reaction (ORR). Here, a new synthetic approach is developed to tune the 3D structure of Pt-based alloys, and switch a synthetic reaction which produces solid PtCu octahedral stars (OSs) to produce PtCu nested skeleton cubes (NSCs) by simple addition of Ni(acac)2 . In particular, Ni2+ -guided anisotropic growth is observed to generate the nested skeleton structure in PtCu NSCs. Ni2+ , though absent from the nanoalloys, not only endows faster Cu reduction kinetics but also acts as a structure-directing agent. Moreover, it is shown that acetic acid treatment of PtCu NSCs/C exposes Pt-rich surface with a fine-tuned Pt d-band center energy and the reduced Cu leaching, resulting in strikingly high activity and stability. Acid-treated PtCu NSCs/C shows a remarkable ORR mass activity of 5.13 A mgPt -1 , about 26 times higher than commercial Pt/C catalyst. This catalyst also exhibits excellent stability with a lower activity decay of 11.5% and the negligible variation in structure after 10 000 cycles.

Targeted killing of tumor cells based on isoelectric point suitable nanoceria-rod with high oxygen vacancies.

Nanozymes have great potential applications in tumor treatment due to their good stability, high biocompatibility, easy preparation and versatility. However, it remains a challenge to design highly active nanozymes with tumor cell targeting. Herein, three nanoceria structures (nanoceria-rod; nanoceria polyhedra, abbreviated as nanoceria-poly.; and nanoceria-cube) with different surface oxygen vacancy concentrations are designed. Among them, nanoceria-rod shows the highest enzyme activity and tumor cell toxicity because of its highest concentration of oxygen vacancies on the surface. Further study shows that nanoceria-rod can selectively enter tumor cells because nanoceria-rod with a suitable isoelectric point (IEP) remains positively charged in the acidic microenvironment of the tumor but negatively charged in the physiological microenvironment of normal cells. Nanoceria-rod distributes in lysosomes and phagosomes to produce reactive oxygen species (ROS) in tumor cells. Finally, the mitochondrial membrane potential (MMP) was reduced, which caused cell apoptosis. This study provides an interesting new tumor-targeting therapy method, which could also be extended to other drug nanocarriers and diagnostic imaging nanomaterials for tumors.

Biomass-Based Carbon-Supported Sulfate Catalyst for Efficient Synthesis of Dimethoxymethane from Direct Oxidation of Dimethyl Ether.

The synthesis of dimethoxymethane (DMM) from direct oxidation of dimethyl ether (DME) is a green and competitive route with good atomic economy and low carbon emission and is also an urgent need. In this work, biomass-based carbon-supported sulfate catalysts were designed and prepared for the efficient synthesis of DMM from DME oxidation. The prepared carbon support from cellulose displayed much larger specific surface area and a developed microporous structure, which effectively benefited a high dispersion of sulfate components, leading to mainly weak acid sites and more oxygen functional groups on the catalyst surface. The Ti(SO4)2/PC-H2SO4 catalyst exhibits excellent performance for DME oxidation with DMM1-2 selectivity up to 96.7%, and DMM selectivity reaches 89.1%, notably higher than that of previously reported results. The distinctive surface structure and chemical properties of the carbon support have important impacts on the dispersion state of sulfate species, affecting the acidic and redox properties of the catalysts.