Close Intimacy between PtIn Clusters and Zeolite Channels for Ultrastability toward Propane Dehydrogenation.

Propane dehydrogenation (PDH) serves as a pivotal intentional technique to produce propylene. The stability of PDH catalysts is generally restricted by the readsorption of propylene which can subsequently undergo side reactions for coke formation. Herein, we demonstrate an ultrastable PDH catalyst by encapsulating PtIn clusters within silicalite-1 which serves as an efficient promoter for olefin desorption. The mean lifetime of PtIn@S-1 (S-1, silicalite-1) was calculated as 37317 h with high propylene selectivity of >97% at 580 °C with a weight hourly space velocity (WHSV) of 4.7 h-1. With an ultrahigh WHSV of 1128 h-1, which pushed the catalyst away from the equilibrium conversion to 13.3%, PtIn@S-1 substantially outperformed other reported PDH catalysts in terms of mean lifetime (32058 h), reaction rates (3.42 molpropylene gcat-1 h-1 and 341.90 molpropylene gPt-1 h-1), and total turnover number (14387.30 kgpropylene gcat-1). The developed catalyst is likely to lead the way to scalable PDH applications.

Cascade Synthesis of Fe-N2-Fe Dual-Atom Catalysts for Superior Oxygen Catalysis.

Dual-atom catalysts (DACs) have been proposed to break the limitation of single-atom catalysts (SACs) in the synergistic activation of multiple molecules and intermediates, offering an additional degree of freedom for catalytic regulation. However, it remains a challenge to synthesize DACs with high uniformity, atomic accuracy, and satisfactory loadings. Herein, we report a facile cascade synthetic strategy for DAC via precise electrostatic interaction control and neighboring vacancy construction. We synthesized well-defined, uniformly dispersed dual Fe sites which were connected by two nitrogen bonds (denoted as Fe-N2-Fe). The as-synthesized DAC exhibited superior catalytic performances towards oxygen reduction reaction, including good half-wave potential (0.91 V), high kinetic current density (21.66 mA cm-2), and perfect durability. Theoretical calculation revealed that the DAC structure effectively tunes the oxygen adsorption configuration and decreases the cleavage barrier, thereby improving the catalytic kinetics. The DAC-based zinc-air batteries exhibited impressive power densities of 169.8 and 52.18 mW cm-2 at 25 oC and -40 oC, which is 1.7 and 2.0 times higher than those based on Pt/C+Ir/C, respectively. We also demonstrated the universality of our strategy in synthesizing other M-N2-M DACs (M= Co, Cu, Ru, Pd, Pt, and Au), facilitating the construction of a DAC library for different catalytic applications.

Symmetry-Breaking Sites for Activating Linear Carbon Dioxide Molecules.

ConspectusCO2 is not only a greenhouse gas but also a pivotal carbon source as a promising supplement to fossil fuels. Both the environment and energy crises have compelled the researchers to explore how to efficiently transform CO2 into liquid fuels and value-added chemicals. As the industrialized approach nowadays, heterogeneous CO2 hydrogenation driven by thermal energy represents a potential strategy to help mitigate the greenhouse effect and reduce the reliance on fossil fuels. However, as the prerequisite for CO2 hydrogenation, CO2 activation is difficult due to the thermodynamic stability and chemical inertness of CO2 molecules. It is not proper to activate CO2 by directly increasing the reaction temperature, because CO2 hydrogenation into liquid products is an exothermic process where elevating the temperature decreases both the balanced conversion of CO2 and the balanced selectivity for target products. Therefore, the key scientific issue for CO2 hydrogenation lies in how to design catalysts which enable efficient activation of CO2. Up to date, a vast variety of active sites have been constructed for effective activation of CO2. These active sites including step sites, alloys, interface, substitution, vacancies, etc. are generally symmetry-breaking rather than perfect flat surfaces.Herein, we propose a catalyst design principle of constructing symmetry-breaking sites to activate nonpolar CO2 molecules. From the perspective of electronic properties, there is a prominent charge density gradient in a symmetry-breaking center, resulting in perturbing electronic structures of nonpolar CO2 and polarizing the adsorbed species. From the perspective of adsorption configuration, a symmetry-breaking site gives a local torque which enables more effective overlapping of atomic orbitals and thus more facilely bending of linear CO2 molecules, compared with symmetric sites. In this Account, we categorize the modes of CO2 activation and put forward the design principle of constructing symmetry-breaking sites. Moreover, we illustrate how to construct symmetry-breaking sites from the perspectives of local and global structures. Strategies to break the symmetry of local structures include surface substitution, surface adatom, and surface vacancy. Strategies to break the symmetry of global structures comprise surface modification with ligands, high-index surface, and phase reconstruction. In the future, further improvements, such as quantified descriptors, function for C-C coupling, and applicability to other nonpolar molecules, are necessary.

Atomic-Level Construction of Tensile-Strained PdFe Alloy Surface toward Highly Efficient Oxygen Reduction Electrocatalysis.

Exploring the high-performance non-Pt electrocatalysts for oxygen reduction reaction (ORR), the bottleneck process in fuel cells, is desirable but challenging. Here, we report the Pd@PdFe core-shell icosahedra as an active and durable electrocatalyst toward ORR in alkaline conditions, which feature a three-atomic-layer tensile-strained PdFe overlayer on Pd icosahedra. Our optimized catalyst shows 2.8-fold enhancement in mass activity and 6.9-fold enhancement in specific activity than commercial Pt/C catalyst toward ORR, representing one of the best non-Pt electrocatalysts. Moreover, the boosted ORR catalysis is strongly supported by the assembled fuel cell performance using Pd@PdFe core-shell icosahedra as the cathode electrocatalyst. The density functional theory calculations reveal that the synergistic coupling of tensile strain and alloy effects enables the optimum binding strength for intermediates, thus causing the maximum activity. The present work suggests the coupling between multiple surface modulations endows larger room for the rational design of remarkable catalysts.

Surface Iron Species in Palladium-Iron Intermetallic Nanocrystals that Promote and Stabilize CO2 Methanation.

It is of pivotal importance to develop efficient catalysts and investigate the intrinsic mechanism for CO2 methanation. Now, it is reported that PdFe intermetallic nanocrystals afforded high activity and stability for CO2 methanation. The mass activity of fct-PdFe nanocrystals reached 5.3 mmol g-1 h-1 , under 1 bar (CO2 :H2 =1:4) at 180 °C, being 6.6, 1.6, 3.3, and 5.3 times as high as that of fcc-PdFe nanocrystals, Ru/C, Ni/C, and Pd/C, respectively. After 20 rounds of successive reaction, 98 % of the original activity was retained for PdFe intermetallic nanocrystals. Further mechanistic studies revealed that PdFe intermetallic nanocrystals enabled the maintenance of metallic Fe species via a reversible oxidation-reduction process in CO2 methanation. The metallic Fe in PdFe intermetallic nanocrystals induced the direct conversion of CO2 into CO* as the intermediate, contributing to the enhanced activity.

One-Nanometer-Thick PtNiRh Trimetallic Nanowires with Enhanced Oxygen Reduction Electrocatalysis in Acid Media: Integrating Multiple Advantages into One Catalyst.

Finding an active and durable catalyst for the acidic oxygen reduction reaction (ORR), a key process for fuel cells, remains an open challenge due to the thermodynamically contradictory requirements for activity and durability. Here, we report that an active and durable ORR catalyst can be achieved by integrating multiple structural and compositional advantages into one catalyst. The mass activity and specific activity of as-obtained 1-nm-thick PtNiRh trimetallic nanowires/C catalyst were 15.2 and 9.7 times as high as that of commercial Pt/C catalyst, respectively. The compressive strain and ligand effects arising from the advantageous microstructure and optimal composition of the nanowires were revealed to enhance the activity. Besides, the PtNiRh trimetallic nanowires/C catalyst exhibited substantially improved durability relative to commercial Pt/C catalyst, due to the combination of its one-dimensional structure and incorporated Rh atoms. This work provides a general guidance for the design of an impressive heterogeneous catalyst.

Achieving Remarkable Activity and Durability toward Oxygen Reduction Reaction Based on Ultrathin Rh-Doped Pt Nanowires.

The research of active and sustainable electrocatalysts toward oxygen reduction reaction (ORR) is of great importance for industrial application of fuel cells. Here, we report a remarkable ORR catalyst with both excellent mass activity and durability based on sub 2 nm thick Rh-doped Pt nanowires, which combine the merits of high utilization efficiency of Pt atoms, anisotropic one-dimensional nanostructure, and doping of Rh atoms. Compared with commercial Pt/C catalyst, the Rh-doped Pt nanowires/C catalyst shows a 7.8 and 5.4-fold enhancement in mass activity and specific activity, respectively. The combination of extended X-ray absorption fine structure analysis and density functional theory calculations reveals that the compressive strain and ligand effect in Rh-doped Pt nanowires optimize the adsorption energy of hydroxyl and in turn enhance the specific activity. Moreover, even after 10000 cycles of accelerated durability test in O2 condition, the Rh-doped Pt nanowires/C catalyst exhibits a drop of 9.2% in mass activity, against a big decrease of 72.3% for commercial Pt/C. The improved durability can be rationalized by the increased vacancy formation energy of Pt atoms for Rh-doped Pt nanowires.

Catalysis-Mediated Male Contraception through Black Phosphorus Nanosheets.

Nanocontraception has been proposed and received extensive attention in recent years for population control. However, currently developed methods for nanocontraception still face problems in efficacy and safety. Here, we propose catalysis-mediated oxidation as a new strategy for nanocontraception. With the catalytic production of highly oxidative species, male contraception was successfully achieved after the administration of black phosphorus nanosheets into the testes of male mice. Further mechanistic studies revealed that contraception was induced by oxidative stress and apoptosis of spermatogenesis cells. Meanwhile, the apoptosis of germ cells released testis antigen and induced immune cell infiltration, which enhanced reproductive damage. Notably, the introduced black phosphorus nanosheets naturally degraded during the catalytic oxidation process and ultimately converted to harmless phosphates, indicating the safety of the strategy. Furthermore, the catalysis-mediated strategy avoids utilizing additional inducers, such as near-infrared irradiation, magnetic fields, or ultrasound, which may cause severe pain. In summary, the proposed catalysis-mediated contraception can be a self-cleared, convenient, and safe strategy for controlling male fertility.

Manipulating local coordination of copper single atom catalyst enables efficient CO2-to-CH4 conversion.

Electrochemical CO2 conversion to methane, powered by intermittent renewable electricity, provides an entrancing opportunity to both store renewable electric energy and utilize emitted CO2. Copper-based single atom catalysts are promising candidates to restrain C-C coupling, suggesting feasibility in further protonation of CO* to CHO* for methane production. In theoretical studies herein, we find that introducing boron atoms into the first coordination layer of Cu-N4 motif facilitates the binding of CO* and CHO* intermediates, which favors the generation of methane. Accordingly, we employ a co-doping strategy to fabricate B-doped Cu-Nx atomic configuration (Cu-NxBy), where Cu-N2B2 is resolved to be the dominant site. Compared with Cu-N4 motifs, as-synthesized B-doped Cu-Nx structure exhibits a superior performance towards methane production, showing a peak methane Faradaic efficiency of 73% at -1.46 V vs. RHE and a maximum methane partial current density of -462 mA cm-2 at -1.94 V vs. RHE. Extensional calculations utilizing two-dimensional reaction phase diagram analysis together with barrier calculation help to gain more insights into the reaction mechanism of Cu-N2B2 coordination structure.

Water enables mild oxidation of methane to methanol on gold single-atom catalysts.

As a 100% atom-economy process, direct oxidation of methane into methanol remains as a grand challenge due to the dilemma between activation of methane and over-oxidation of methanol. Here, we report that water enabled mild oxidation of methane into methanol with >99% selectivity over Au single atoms on black phosphorus (Au1/BP) nanosheets under light irradiation. The mass activity of Au1/BP nanosheets reached 113.5 µmol gcatal-1 in water pressured with 33 bar of mixed gas (CH4:O2 = 10:1) at 90 °C under light irradiation (1.2 W), while the activation energy was 43.4 kJ mol-1. Mechanistic studies revealed that water assisted the activation of O2 to generate reactive hydroxyl groups and •OH radicals under light irradiation. Hydroxyl groups reacted with methane at Au single atoms to form water and CH3* species, followed by oxidation of CH3* via •OH radicals into methanol. Considering the recycling of water during the whole process, we can also regard water as a catalyst.

Static Regulation and Dynamic Evolution of Single-Atom Catalysts in Thermal Catalytic Reactions.

Single-atom catalysts provide an ideal platform to bridge the gap between homogenous and heterogeneous catalysts. Here, the recent progress in this field is reported from the perspectives of static regulation and dynamic evolution. The syntheses and characterizations of single-atom catalysts are briefly discussed as a prerequisite for catalytic investigation. From the perspective of static regulation, the metal-support interaction is illustrated in how the supports alter the electronic properties of single atoms and how the single atoms activate the inert atoms in supports. The synergy between single atoms is highlighted. Besides these static views, the surface reconstruction, such as displacement and aggregation of single atoms in catalytic conditions, is summarized. Finally, the current technical challenges and mechanistic debates in single-atom heterogeneous catalysts are discussed.

2D Behaviors of Excitons in Cesium Lead Halide Perovskite Nanoplatelets.

Fundamental to understanding and predicting the optoelectronic properties of semiconductors is the basic parameters of excitons such as oscillator strength and exciton binding energy. However, such knowledge of CsPbBr3 perovskite, a promising optoelectronic material, is still unexplored. Here we demonstrate that quasi-two-dimensional (quasi-2D) CsPbBr3 nanoplatelets (NPLs) with 2D exciton behaviors serve as an ideal system for the determination of these parameters. It is found that the oscillator strength of CsPbBr3 NPLs is up to 1.18 × 104, higher than that of colloidal II-VI NPLs and epitaxial quantum wells. Furthermore, the exciton binding energy is determined to be of ∼120 meV from either the optical absorption or the photoluminescence analysis, comparable to that reported in colloidal II-VI quantum wells. Our work provides physical understanding of the observed excellent optical properties of CsPbBr3 nanocrystals and would benefit the prediction of high-performance excitonic devices based on such materials.

Atomically thin cesium lead bromide perovskite quantum wires with high luminescence.

We report a room-temperature colloidal synthesis of few-unit-cell-thick CsPbBr3 QWs with lengths over a hundred nanometers. The surfactant-directed oriented attachment growth mechanism was proposed to explain the formation of such CsPbBr3 QWs. Owing to the strong quantum confinement effect, the photoluminescence (PL) emission peak of few-unit-cell-thick CsPbBr3 QWs blue-shifted to 430 nm. The ensemble PL quantum yield (PLQY) of the few-unit-cell-thick CsPbBr3 QWs increased to 21.13% through a simple heat-treatment process. The improvement of PLQY was ascribed to the reduction of the density of surface trap states and defect states induced by the heat-treatment process. Notably, the dependence of the bandgap on the diameter with different numbers of unit cells was presented for the first time in 1-D CsPbBr3 QWs on the basis of the produced few-unit-cell-thick CsPbBr3 QWs.