Pulse Electrolysis Turns on CO2 Methanation through N-Confused Cupric Porphyrin.

Breaking the D4h symmetry in the square-planar M-N4 configuration of macrocycle molecular catalysts has witnessed enhanced electrocatalytic activity, but at the expense of electrochemical stability. Herein, we hypothesize that the lability of the active Cu-N3 motifs in the N-confused copper (II) tetraphenylporphyrin (CuNCP) could be overcome by applying pulsed potential electrolysis (PPE) during electrocatalytic carbon dioxide reduction. We find that applying PPE can indeed enhance the CH4 selectivity on CuNCP by 3 folds to reach the partial current density of 170 mA cm-2 at >60 % Faradaic efficiency (FE) in flow cell. However, combined ex situ X-ray diffraction (XRD), transmission electron microscope (TEM), and in situ X-ray absorption spectroscopy (XAS), infrared (IR), Raman, scanning electrochemical microscopy (SECM) characterizations reveal that, in a prolonged time scale, the decomplexation of CuNCP is unavoidable, and the promoted water dissociation under high anodic bias with lowered pH and enriched protons facilitates successive hydrogenation of *CO on the irreversibly reduced Cu nanoparticles, leading to the improved CH4 selectivity. As a key note, this study signifies the adaption of electrolytic protocol to the catalyst structure for tailoring local chemical environment towards efficient CO2 reduction.

Proton Shuttling by Polyaniline of High Brønsted Basicity for Improved Electrocatalytic Ethylene Production from CO2.

Hybrid organic/inorganic composites with the organic phase tailored to modulate local chemical environment at the Cu surface arise as an enchanting category of catalysts for electrocatalytic CO2 reduction reaction (CO2 RR). A fundamental understanding on how the organics of different functionality, polarity, and hydrophobicity affect the reaction path is, however, still lacking to guide rational catalyst design. Herein, polypyrrole (PPy) and polyaniline (PANI) manifesting different Brønsted basicity are compared for their regulatory roles on the CO2 RR pathways regarding *CO coverage, proton source and interfacial polarity. Concerted efforts from in situ IR, Raman and operando modelling unveil that at the PPy/Cu interface with limited *CO coverage, hydridic *H produced by the Volmer step favors the carbon hydrogenation of *CO to form *CHO through a Tafel process; Whereas at the PANI/Cu interface with concentrated CO2 and high *CO coverage, protonic H+ shuttled through the benzenoid -NH- protonates the oxygen of *CO, yielding *COH for asymmetric coupling with nearby *CO to form *OCCOH under favored energetics. As a result of the tailored chemical environment, the restructured PANI/Cu composite demonstrates a high partial current density of 0.41 A cm-2 at a maximal Faraday efficiency of 67.5 % for ethylene production, ranking among states of the art.

The Role of Bismuth in Suppressing the CO Poisoning in Alkaline Methanol Electrooxidation: Switching the Reaction from the CO to Formate Pathway.

While tuning the electronic structure of Pt can thermodynamically alleviate CO poisoning in direct methanol fuel cells, the impact of interactions between intermediates on the reaction pathway is seldom studied. Herein, we contrive a PtBi model catalyst and realize a complete inhibition of the CO pathway and concurrent enhancement of the formate pathway in the alkaline methanol electrooxidation. The key role of Bi is enriching OH adsorbates (OHad) on the catalyst surface. The competitive adsorption of CO adsorbates (COad) and OHad at Pt sites, complementing the thermodynamic contribution from alloying Bi with Pt, switches the intermediate from COad to formate that circumvents CO poisoning. Hence, 8% Bi brings an approximately 6-fold increase in activity compared to pure Pt nanoparticles. This notion can be generalized to modify commercially available Pt/C catalysts by a microwave-assisted method, offering opportunities for the design and practical production of CO-tolerance electrocatalysts in an industrial setting.

Encapsulated Metal Nanoparticles for Catalysis.

Metal nanoparticles have drawn great attention in heterogeneous catalysis. One challenge is that they are easily deactivated by migration-coalescence during the catalysis process because of their high surface energy. With the rapid development of nanoscience, encapsulating metal nanoparticles in nanoshells or nanopores becomes one of the most promising strategies to overcome the stability issue of the metal nanoparticles. Besides, the activity and selectivity could be simultaneously enhanced by taking advantage of the synergy between the metal nanoparticles and the encapsulating materials as well as the molecular sieving property of the encapsulating materials. In this review, we provide a comprehensive summary of the recent progress in the synthesis and catalytic properties of the encapsulated metal nanoparticles. This review begins with an introduction to the synthetic strategies for encapsulating metal nanoparticles with different architectures developed to date, including their encapsulation in nanoshells of inorganic oxides and carbon, porous materials (zeolites, metal-organic frameworks, and covalent organic frameworks), and organic capsules (dendrimers and organic cages). The advantages of the encapsulated metal nanoparticles are then discussed, such as enhanced stability and recyclability, improved selectivity, strong metal-support interactions, and the capability of enabling tandem catalysis, followed by the introduction of some representative applications of the encapsulated metal nanoparticles in thermo-, photo-, and electrocatalysis. At the end of this review, we discuss the remaining challenges associated with the encapsulated metal nanoparticles and provide our perspectives on the future development of the field.

Bismuth Oxyhydroxide-Pt Inverse Interface for Enhanced Methanol Electrooxidation Performance.

Developing efficient Pt-based electrocatalysts for the methanol oxidation reaction (MOR) is of pivotal importance for large-scale application of direct methanol fuel cells (DMFCs), but Pt suffers from severe deactivation brought by the carbonaceous intermediates such as CO. Here, we demonstrate the formation of a bismuth oxyhydroxide (BiOx(OH)y)-Pt inverse interface via electrochemical reconstruction for enhanced methanol oxidation. By combining density functional theory calculations, X-ray absorption spectroscopy, ambient pressure X-ray photoelectron spectroscopy, and electrochemical characterizations, we reveal that the BiOx(OH)y-Pt inverse interface can induce the electron deficiency of neighboring Pt; this would result in weakened CO adsorption and strengthened OH adsorption, thereby facilitating the removal of the poisonous intermediates and ensuring the high activity and good stability of Pt2Bi sample. This work provides a comprehensive understanding of the inverse interface structure and deep insight into the active sites for MOR, offering great opportunities for rational fabrication of efficient electrocatalysts for DMFCs.

Integrated Evaporator for Efficient Solar-Driven Interfacial Steam Generation.

Solar-driven interfacial steam generation is a promising technique for clean water production because it can minimize thermal loss by localizing solar-to-heat conversion at the air/liquid interface. Here we report an integrated solar evaporator by partially growing 2D polypyrrole microsheets within a melamine foam through chemical vapor polymerization. These microsheets can induce multiple light reflections within the foam, enable omnidirectional light absorption, provide abundant surfaces to promote heat transfer, and achieve spatially defined hydrophobicity to facilitate vapor escape. Meanwhile, the inherent hydrophilicity of the bottom part of the foam promotes spontaneous upward water transport and suppresses heat loss. The composite foam exhibits an excellent apparent evaporation rate of ∼2 kg/(m2·h) and solar-to-vapor efficiency of ∼91%. The combined advantages of large surface area, high efficiency, low cost, all-weather application, excellent durability, and scalable manufacturing make our integrated design promising for fabricating large-scale solar steam generation systems that are suitable for practical clean water production.

Bi(OH)3/PdBi Composite Nanochains as Highly Active and Durable Electrocatalysts for Ethanol Oxidation.

Developing high-performance electrocatalysts for the ethanol oxidation reaction (EOR) is critical to the commercialization of direct ethanol fuel cells. However, current EOR catalysts suffer from high cost, low activity, and poor durability. Here we report the preparation of PdBi-Bi(OH)3 composite nanochains with outstanding EOR activity and durability. The incorporation of Bi can tune the electronic structure and downshift the d-band center of Pd while the surface decoration of Bi(OH)3 can facilitate the oxidative removal of CO and other carbonaceous intermediates. As a result, the nanochains manifest an exceptional mass activity (5.30 A mgPd-1, 4.6-fold higher than that of commercial Pd/C) and outstanding durability (with a retained current density of ∼1.00 A mgPd-1 after operating for 20 000 s). More importantly, the nanochain catalyst can be reactivated, and negligible activity loss has been observed after operating for 200 000 s with periodic reactivation, making it one of the best EOR catalysts.

Self-Aligned Anisotropic Plasmonic Nanostructures.

Great opportunities emerge not only in the generation of anisotropic plasmonic nanostructures but also in controlling their orientation relative to incident light. Herein, a stepwise seeded growth method is reported for the synthesis of rod-shaped plasmon nanostructures which are vertically self-aligned with respect to the surface of colloidal substrates. Anisotropic growth of metal nanostructure is achieved by depositing metal seeds onto the surface of colloidal substrates and then selectively passivating the seed surface to induce symmetry breaking in the subsequent seed-mediated growth process. The versatility of this method is demonstrated by producing nanoparticle dimers and linear trimers of Au, Au-Ag, Au-Pd, and Au-Cu2 O. Further, this unique method enables the automatic vertical alignment of the resulting plasmonic nanostructures to the surface of the colloidal substrate, thereby making it possible to design magnetic/plasmonic nanocomposites that allow the dynamic tuning of the plasmon excitation by controlling their orientation using an external magnetic field. The controlled anisotropic growth of colloidal plasmonic nanostructures and their dynamic modulation of plasmon excitation further allow them to be conveniently fixed in a thin polymer film with a well-controlled orientation to display polarization-dependent patterns that may find important applications in information encryption.

Noble-Metal-Free Electrocatalysts for Oxygen Evolution.

Oxygen evolution reaction (OER) plays a vital role in many energy conversion and storage processes including electrochemical water splitting for the production of hydrogen and carbon dioxide reduction to value-added chemicals. IrO2 and RuO2 , known as the state-of-the-art OER electrocatalysts, are severely limited by the high cost and low earth abundance of these noble metals. Developing noble-metal-free OER electrocatalysts with high performance has been in great demand. In this review, recent advances in the design and synthesis of noble-metal-free OER electrocatalysts including Ni, Co, Fe, Mn-based hydroxides/oxyhydroxides, oxides, chalcogenides, nitrides, phosphides, and metal-free compounds in alkaline, neutral as well as acidic electrolytes are summarized. Perspectives are also provided on the fabrication, evaluation of OER electrocatalysts and correlations between the structures of the electrocatalysts and their OER activities.

In situ one-step synthesis of Fe3O4@MIL-100(Fe) core-shells for adsorption of methylene blue from water.

A new route for Fe3O4@MIL-100(Fe) core-shells is proposed via in situ one-step hydrothermal strategy, in which Fe3O4 microspheres not only serve as magnetic cores but also provide Fe(III) for MIL-100(Fe) synthesis. The MIL-100(Fe) is uniformly grown as a shell on the surface of Fe3O4, and the shell thickness can be fine-tuned from 73.5 to 148nm by simply controlling the reaction time. Compared with Fe3O4, the surface area and pore volume of the Fe3O4@MIL-100(Fe) are significantly increased while the magnetism is barely affected. The application of Fe3O4@MIL-100(Fe) in adsorption was tested using several dyes as model analytes, and showed high adsorption capacity (221mgg-1) towards methylene blue (MB), which is based on electrostatic interactions and size filter effect. The MB adsorption isotherm follows Langmuir model and pseudo second-order kinetic model. Intra-particle diffusion model reveals that both film and pore diffusions are involved in the rate limiting steps. The adsorption is controlled by enthalpy change rather than entropy effect. ΔH, ΔS and ΔG values indicated that the adsorption process was spontaneous and exothermic. Simple synthesis procedure, immense magnetism, high adsorption capacity and excellent reusability of Fe3O4@MIL-100(Fe) make it an attractive candidate for application of MB removal from polluted environmental samples.

Phase-controllable synthesis of cobalt hydroxide for electrocatalytic oxygen evolution.

Identification of active sites for oxygen evolution reaction (OER) plays a key role in the design and fabrication of high-performance cobalt-based electrocatalysts. Herein, we report the synthesis of two types of two-dimensional monometallic cobalt hydroxide nanoplates in aqueous solution for OER: α-Co(OH)2 with both Co2+Td and Co2+Oh sites and ß-Co(OH)2 with Co2+Oh sites. Electrochemical characterization reveals that α-Co(OH)2 is more active than ß-Co(OH)2 towards OER. The better activity can be attributed to the presence of Co2+Td sites in α-Co(OH)2, which are more active than Co2+Oh sites. Our finding clarifies the contribution of the two catalytic sites and helps future rational design of high-performance OER electrocatalysts.

Photocatalytic Color Switching of Transition Metal Hexacyanometalate Nanoparticles for High-Performance Light-Printable Rewritable Paper.

Developing efficient photoreversible color switching systems for constructing rewritable paper is of significant practical interest owing to the potential environmental benefits including forest conservation, pollution reduction, and resource sustainability. Here we report that the color change associated with the redox chemistry of nanoparticles of Prussian blue and its analogues could be integrated with the photocatalytic activity of TiO2 nanoparticles to construct a class of new photoreversible color switching systems, which can be conveniently utilized for fabricating ink-free, light printable rewritable paper with various working colors. The current system also addresses the phase separation issue of the previous organic dye-based color switching system so that it can be conveniently applied to the surface of conventional paper to produce an ink-free light printable rewritable paper that has the same feel and appearance as the conventional paper. With its additional advantages such as excellent scalability and outstanding rewriting performance (reversibility >80 times, legible time >5 days, and resolution >5 µm), this novel system can serve as an eco-friendly alternative to regular paper in meeting the increasing global needs for environment protection and resource sustainability.

Design of two-dimensional, ultrathin MoS2 nanoplates fabricated within one-dimensional carbon nanofibers with thermosensitive morphology: high-performance electrocatalysts for the hydrogen evolution reaction.

Two-dimensional MoS2 nanoplates within carbon nanofibers (CNFs) with monolayer thickness, nanometer-scale dimensions and abundant edges are fabricated. This strategy provides a well-defined pathway for the precise design of MoS2 nanomaterials, offering control over the evolution of MoS2 morphology from nanoparticles to nanoplates as well as from mono- to several-layer structures, over a lateral dimension range of 5 to 70 nm. CNFs play an important role in confining the growth of MoS2 nanoplates, leading to increases in the amount of exposed edge sites while hindering the stacking and aggregation of MoS2 layers, and accelerating electron transfer. The controlled growth of MoS2 nanoplates embedded in CNFs is leveraged to demonstrate structure-dependent catalytic activity in the hydrogen evolution reaction (HER). The results suggest that increases in the number of layers and the lateral dimension result in a decrease in HER activity as a general rule. Single-layer MoS2 nanoplates with abundant edges and a lateral dimension of 7.3 nm demonstrated the lowest hydrogen evolution reaction overpotential of 93 mV (J = 10 mA/cm(2)), the highest current density of 80.3 mA/cm(2) at η = 300 mV and the smallest Tafel slope of 42 mV/decade. The ability of MoS2-CNFs hybrids to act as nonprecious metal catalysts indicates their promise for use in energy-related electrocatalytic applications.