Activating Inert Crystal Face via Facet-Dependent Quench-Engineering for Electrocatalytic Water Oxidation.

Developing a facile strategy to activate the inert crystal face of an electrocatalyst is critical to full-facet utilization, yet still challenging. Herein, the electrocatalytic activity of the inert crystal face is activated by quenching Co3O4 cubes and hexagonal plates with different crystal faces in Fe(NO3)3 solution, and the regulation mechanism of facet-dependent quench-engineering is further revealed. Compared to the Co3O4 cube with exposed {100} facet, the Co3O4 hexagonal plate with exposed {111} facet is more responsive to quenching, accompanied by a rougher surface, richer defect, and more Fe doping. Theoretical calculations indicate that the {111} facet has a more open structure with lower defect formation energy and Fe doping energy, ensuring its electronic and coordination structure is easier to optimize. Therefore, quench-engineering largely increases the catalytic activity of {111) facet for oxygen evolution reaction by 13.2% (the overpotential at 10 mA cm-2 decreases from 380 to 330 mV), while {100} facet only increases by 7.6% (from 393 to 363 mV). The quenched Co3O4 hexagonal plate exhibits excellent electrocatalytic activity and stability in both zinc-air battery and water-splitting. The work reveals the influence mechanism of crystal face on quench-engineering and inspires the activation of the inert crystal face.

Hydrogen Spillover Induced PtCo/CoOx Interfaces with Enhanced Catalytic Activity for CO Oxidation at Low Temperatures in Humid Conditions.

The development of catalysts with abundant active interfaces for superior low-temperature catalytic CO oxidation is critical to meet increasingly rigorous emission requirements, yet still challenging. Herein, this work reports a PtCo/CoOx/Al2O3 catalyst with PtCo clusters and enriched Pt─O─Co interfaces induced by hydrogen spillover from the Pt sites and self-oxidation process in air, exhibiting excellent performance for CO oxidation at low temperatures and humid conditions. The combination of structural characterizations and in situ Fourier transform infrared spectroscopy reveals that the PtCo cluster effectively prevents CO saturation/poisoning on the Pt surface. Additionally, the presence of Pt─O─Co interfaces in the PtCo/CoOx/Al2O3 catalyst provides a significant number of active sites for oxygen activation and ─OH formation. This facilitates efficient generation of CO2 at ambient temperature by coupling with nearby adsorbed CO molecules, resulting in superior low-temperature activity and long-term stability for CO oxidation under humid conditions. This work provides a facile route toward rationalizing the design of catalysts with more active interfaces for superior low-temperature CO oxidation under humid conditions for practical applications.

Efficient Photothermal Catalytic Oxidation Enabled by Three-Dimensional Nanochannel Substrates.

Photothermal catalysis exhibits promising prospects to overcome the shortcomings of high-energy consumption of traditional thermal catalysis and the low efficiency of photocatalysis. However, there is still a challenge to develop catalysts with outstanding light absorption capability and photothermal conversion efficiency for the degradation of atmospheric pollutants. Herein, we introduced the Co3O4 layer and Pt nanoclusters into the three-dimensional (3D) porous membrane through the atomic layer deposition (ALD) technique, leading to a Pt/Co3O4/AAO monolithic catalyst. The 3D ordered nanochannel structure can significantly enhance the solar absorption capacity through the light-trapping effect. Therefore, the embedded Pt/Co3O4 catalyst can be rapidly heated and the O2 adsorbed on the Pt clusters can be activated to generate sufficient O2- species, exhibiting outstanding activity for the diverse VOCs (toluene, acetone, and formaldehyde) degradation. Optical characterization and simulation calculation confirmed that Pt/Co3O4/AAO exhibited state-of-the-art light absorption and a notable localized surface plasmon resonance (LSPR) effect. In situ diffuse reflectance infrared Fourier transform spectrometry (in situ DRIFTS) studies demonstrated that light irradiation can accelerate the conversion of intermediates during toluene and acetone oxidation, thereby inhibiting byproduct accumulation. Our finding extends the application of AAO's optical properties in photothermal catalytic degradation of air pollutants.

Tailoring Metal-Oxygen Bonds Boosts Oxygen Reaction Kinetics for High-Performance Zinc-Air Batteries.

Metal-oxygen bonds significantly affect the oxygen reaction kinetics of metal oxide-based catalysts but still face the bottlenecks of limited cognition and insufficient regulation. Herein, we develop a unique strategy to accurately tailor metal-oxygen bond structure via amorphous/crystalline heterojunction realized by ion-exchange. Compared with pristine amorphous CoSnO3-y, iron ion-exchange induced amorphous/crystalline structure strengthens the Sn-O bond, weakens the Co-O bond strength, and introduces additional Fe-O bond, accompanied by abundant cobalt defects and optimal oxygen defects with larger pore structure and specific surface area. The optimization of metal-oxygen bond structure is dominated by the introduction of crystal structure and further promoted by the introduction of Fe-O bond and rich Co defect. Remarkably, the Fe doped amorphous/crystalline catalyst (Co1-xSnO3-y-Fe0.021-A/C) demonstrates excellent oxygen evolution reaction and oxygen reduction reaction activities with a smaller potential gap (ΔE = 0.687 V), and the Zn-air battery based with Co1-xSnO3-y-Fe0.021-A/C exhibits excellent output power density, cycle performance, and flexibility.

Toward More Efficient Carbon-Based Electrocatalysts for Hydrogen Peroxide Synthesis: Roles of Cobalt and Carbon Defects in Two-Electron ORR Catalysis.

Electrochemical production of H2O2 is a cost-effective and environmentally friendly alternative to the anthraquinone-based processes. Metal-doped carbon-based catalysts are commonly used for 2-electron oxygen reduction reaction (2e-ORR) due to their high selectivity. However, the exact roles of metals and carbon defects on ORR catalysts for H2O2 production remain unclear. Herein, by varying the Co loading in the pyrolysis precursor, a Co-N/O-C catalyst with Faradaic efficiency greater than 90% in alkaline electrolyte was obtained. Detailed studies revealed that the active sites in the Co-N/O-C catalysts for 2e-ORR were carbon atoms in C-O-C groups at defect sites. The direct contribution of cobalt single atom sites and metallic Co for the 2e-ORR performance was negligible. However, Co plays an important role in the pyrolytic synthesis of a catalyst by catalyzing carbon graphitization, tuning the formation of defects and oxygen functional groups, and controlling O and N concentrations, thereby indirectly enhancing 2e-ORR performance.

Strain-Engineering of Mesoporous Cs3 Bi2 Br9 /BiVO4 S-Scheme Heterojunction for Efficient CO2 Photoreduction.

Slow charge kinetics and unfavorable CO2 adsorption/activation strongly inhibit CO2 photoreduction. In this study, a strain-engineered Cs3 Bi2 Br9 /hierarchically porous BiVO4 (s-CBB/HP-BVO) heterojunction with improved charge separation and tailored CO2 adsorption/activation capability is developed. Density functional theory calculations suggest that the presence of tensile strain in Cs3 Bi2 Br9 can significantly downshift the p-band center of the active Bi atoms, which enhances the adsorption/activation of inert CO2 . Meanwhile, in situ irradiation X-ray photoelectron spectroscopy and electron spin resonance confirm that efficient charge transfer occurs in s-CBB/HP-BVO following an S-scheme with built-in electric field acceleration. Therefore, the well-designed s-CBB/HP-BVO heterojunction exhibits a boosted photocatalytic activity, with a total electron consumption rate of 70.63 µmol g-1 h-1 , and 79.66% selectivity of CO production. Additionally, in situ diffuse reflectance infrared Fourier transform spectroscopy reveals that CO2 photoreduction undergoes a formaldehyde-mediated reaction process. This work provides insight into strain engineering to improve the photocatalytic performance of halide perovskite.

Reversible Stacking of 2D ZnIn2 S4 Atomic Layers for Enhanced Photocatalytic Hydrogen Evolution.

It is technically challenging to reversibly tune the layer number of 2D materials in the solution. Herein, a facile concentration modulation strategy is demonstrated to reversibly tailor the aggregation state of 2D ZnIn2 S4 (ZIS) atomic layers, and they are implemented for effective photocatalytic hydrogen (H2 ) evolution. By adjusting the colloidal concentration of ZIS (ZIS-X, X = 0.09, 0.25, or 3.0 mg mL-1 ), ZIS atomic layers exhibit the significant aggregation of (006) facet stacking in the solution, leading to the bandgap shift from 3.21 to 2.66 eV. The colloidal stacked layers are further assembled into hollow microsphere after freeze-drying the solution into solid powders, which can be redispersed into colloidal solution with reversibility. The photocatalytic hydrogen evolution of ZIS-X colloids is evaluated, and the slightly aggregated ZIS-0.25 displays the enhanced photocatalytic H2 evolution rates (1.11 µmol m-2 h-1 ). The charge-transfer/recombination dynamics are characterized by time-resolved photoluminescence (TRPL) spectroscopy, and ZIS-0.25 displays the longest lifetime (5.55 µs), consistent with the best photocatalytic performance. This work provides a facile, consecutive, and reversible strategy for regulating the photo-electrochemical properties of 2D ZIS, which is beneficial for efficient solar energy conversion.

CuC(O) Interfaces Deliver Remarkable Selectivity and Stability for CO2 Reduction to C2+ Products at Industrial Current Density of 500 mA cm-2.

The electrocatalytic CO2 reduction reaction (CO2 RR) is an attractive technology for CO2 valorization and high-density electrical energy storage. Achieving a high selectivity to C2+ products, especially ethylene, during CO2 RR at high current densities (>500 mA cm-2 ) is a prized goal of current research, though remains technically very challenging. Herein, it is demonstrated that the surface and interfacial structures of Cu catalysts, and the solid-gas-liquid interfaces on gas-diffusion electrode (GDE) in CO2 reduction flow cells can be modulated to allow efficient CO2 RR to C2+ products. This approach uses the in situ electrochemical reduction of a CuO nanosheet/graphene oxide dots (CuOC(O)) hybrid. Owing to abundant CuOC interfaces in the CuOC(O) hybrid, the CuO nanosheets are topologically and selectively transformed into metallic Cu nanosheets exposing Cu(100) facets, Cu(110) facets, Cu[n(100) × (110)] step sites, and Cu+ /Cu0 interfaces during the electroreduction step, the faradaic efficiencie (FE) to C2+ hydrocarbons was reached as high as 77.4% (FEethylene  ≈ 60%) at 500 mA cm-2 . In situ infrared spectroscopy and DFT simulations demonstrate that abundant Cu+ species and Cu0 /Cu+ interfaces in the reduced CuOC(O) catalyst improve the adsorption and surface coverage of *CO on the Cu catalyst, thus facilitating CC coupling reactions.

Quenching-Induced Defect-Rich Platinum/Metal Oxide Catalysts Promote Catalytic Oxidation.

Enhancing oxygen activation through defect engineering is an effective strategy for boosting catalytic oxidation performance. Herein, we demonstrate that quenching is an effective strategy for preparing defect-rich Pt/metal oxide catalysts with superior catalytic oxidation activity. As a proof of concept, quenching of α-Fe2O3 in aqueous Pt(NO3)2 solution yielded a catalyst containing Pt single atoms and clusters over defect-rich α-Fe2O3 (Pt/Fe2O3-Q), which possessed state-of-the-art activity for toluene oxidation. Structural and spectroscopic analyses established that the quenching process created abundant lattice defects and lattice dislocations in the α-Fe2O3 support, and stronger electronic interactions between Pt species and Fe2O3 promote the generation of higher oxidation Pt species to modulate the adsorption/desorption behavior of reactants. In situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) characterization studies and density functional theory (DFT) calculations determined that molecular oxygen and Fe2O3 lattice oxygen were both activated on the Pt/Fe2O3-Q catalyst. Pt/CoMn2O4, Pt/MnO2, and Pt/LaFeO3 catalysts synthesized by the quenching method also offered superior catalytic activity for toluene oxidation. Results encourage the wider use of quenching for the preparation of highly active oxidation catalysts.

Activating Metal Oxides Nanocatalysts for Electrocatalytic Water Oxidation by Quenching-Induced Near-Surface Metal Atom Functionality.

Developing a reliable strategy for the modulation of the texture, composition, and electronic structure of electrocatalyst surfaces is crucial for electrocatalytic performance, yet still challenging. Herein, we develop a facile and universal strategy, quenching, to precisely tailor the surface chemistry of metal oxide nanocatalysts by rapidly cooling them in a salt solution. Taking NiMoO4 nanocatalysts an example, we successfully produce the quenched nanocatalysts offering a greatly reduced oxygen evolution reaction (OER) overpotential by 85 mV and 135 mV at 10 mA cm-2 and 100 mA cm-2 respectively. Through detailed characterization studies, we establish that quenching induces the formation of numerous disordered stepped surfaces and the near-surface metal ions doping, thus regulating the local electronic structures and coordination environments of Ni, Mo, which promotes the formation of the dual-site active and thereby affords a low energy pathway for OER. This quenching strategy is also successfully applied to a number of other metal oxides, such as spinel-type Co3O4, Fe2O3, LaMnO3, and CoSnO3, with similar surface modifications and gains in OER activity. Our finding provides a new inspiration to activate metal oxide catalysts and extends the use of quenching chemistry in catalysis.

Recent Progress of Thermocatalytic and Photo/Thermocatalytic Oxidation for VOCs Purification over Manganese-based Oxide Catalysts.

Volatile organic compounds (VOCs) are one of the main sources of air pollution, which are of wide concern because of their toxicity and serious threat to the environment and human health. Catalytic oxidation has been proven to be a promising and effective technology for VOCs abatement in the presence of heat or light. As environmentally friendly and low-cost materials, manganese-based oxides are the most competitive and promising candidates for the catalytic degradation of VOCs in thermocatalysis or photo/thermocatalysis. This article summarizes the research and development on various manganese-based oxide catalysts, with emphasis on their thermocatalytic and photo/thermocatalytic purification of VOCs in recent years in detail. Single manganese oxides, manganese-based oxide composites, as well as improving strategies such as morphology regulation, heterojunction engineering, and surface decoration by metal doping or universal acid treatment are reviewed. Besides, manganese-based monoliths for practical VOCs abatementare also discussed. Meanwhile, relevant catalytic mechanisms are also summarized. Finally, the existing problems and prospect of manganese-based oxide catalysts for catalyzing combustion of VOCs are proposed.

Upcycling of Electroplating Sludge into Ultrafine Sn@C Nanorods with Highly Stable Lithium Storage Performance.

Sn-based anode materials have become potential substitutes for commercial graphite anode due to their high specific capacity and good safety. In this paper, ultrafine Sn nanoparticles embedded in nitrogen and phosphorus codoped porous carbon nanorods (Sn@C) are obtained by carbonizing bacteria that adsorb the Sn electroplating sludge extracting solution. The as-prepared Sn@C rod-shaped composite exhibits superior electrochemical Li-storage performances, such as a reversible capacity of approximate 560 mAh/g at 1 A/g and an ultralong cycle life exceeding 1500 cycles, with approximately no capacity decay. The ultrastable structure of the Sn@C was revealed using in situ transmission electron microscope at the nanoscale and indicated that the Sn@C composite could restrict the volume expansion of Sn nanoparticles during the lithiation/delithiation cycles. This work provides a new insight into addressing the electroplating sludge and designing novel lithium ion battery anodes.

Boron Doping of Multiwalled Carbon Nanotubes Significantly Enhances Hole Extraction in Carbon-Based Perovskite Solar Cells.

Compared to the conventional perovskite solar cells (PSCs) containing hole-transport materials (HTM), carbon materials based HTM-free PSCs (C-PSCs) have often suffered from inferior power conversion efficiencies (PCEs) arising at least partially from the inefficient hole extraction at the perovskite-carbon interface. Here, we show that boron (B) doping of multiwalled carbon nanotubes (B-MWNTs) electrodes are superior in enabling enhanced hole extraction and transport by increasing work function, carrier concentration, and conductivity of MWNTs. The C-PSCs prepared using the B-MWNTs as the counter electrodes to extract and transport hole carriers have achieved remarkably higher performances than that with the undoped MWNTs, with the resulting PCE being considerably improved from 10.70% (average of 9.58%) to 14.60% (average of 13.70%). Significantly, these cells show negligible hysteretic behavior. Moreover, by coating a thin layer of insulating aluminum oxide (Al2O3) on the mesoporous TiO2 film as a physical barrier to substantially reduce the charge losses, the PCE has been further pushed to 15.23% (average 14.20%). Finally, the impressive durability and stability of the prepared C-PSCs were also testified under various conditions, including long-term air exposure, heat treatment, and high humidity.

In Situ Electrochemically Derived Nanoporous Oxides from Transition Metal Dichalcogenides for Active Oxygen Evolution Catalysts.

Transition metal dichalcogenides have been widely studied as active electrocatalysts for hydrogen evolution reactions. However, their properties as oxygen evolution reaction catalysts have not been fully explored. In this study, we systematically investigate a family of transition metal dichalcogenides (MX, M = Co, Ni, Fe; X = S, Se, Te) as candidates for water oxidation. It reveals that the transition metal dichalcogenides are easily oxidized in strong alkaline media via an in situ electrochemical oxidation process, producing nanoporous transition metal oxides toward much enhanced water oxidation activity due to their increased surface area and more exposed electroactive sites. The optimal cobalt nickel iron oxides that derived from their sulfides and selenides demonstrate a low overpotential of 232 mV at current density of 10 mA cm-2, a small Tafel slope of 35 mV per decade, and negligible degradation of electrochemical activity over 200 h of electrolysis. This study represents the discovery of nanoporous transition metal oxides deriving from their chalcogenides as outstanding electrocatalysts for water oxidation.

Nanofiber Air Filters with High-Temperature Stability for Efficient PM2.5 Removal from the Pollution Sources.

Here, we developed high-efficiency (>99.5%) polyimide-nanofiber air filters for the high temperature PM2.5 removal. The polyimide nanofibers exhibited high thermal stability, and the PM2.5 removal efficiency was kept unchanged when temperature ranged from 25-370 °C. These filters had high air flux with very low pressure drop. They could continuously work for >120 h for PM2.5 index >300. A field-test showed that they could effectively remove >99.5% PM particles from car exhaust at high temperature.

Synthesis, Crystal Structure, and Electrochemical Properties of a Simple Magnesium Electrolyte for Magnesium/Sulfur Batteries.

Most simple magnesium salts tend to passivate the Mg metal surface too quickly to function as electrolytes for Mg batteries. In the present work, an electroactive salt [Mg(THF)6 ][AlCl4 ]2 was synthesized and structurally characterized. The Mg electrolyte based on this simple mononuclear salt showed a high Mg cycling efficiency, good anodic stability (2.5 V vs. Mg), and high ionic conductivity (8.5 mS cm(-1) ). Magnesium/sulfur cells employing the as-prepared electrolyte exhibited good cycling performance over 20 cycles in the range of 0.3-2.6 V, thus indicating an electrochemically reversible conversion of S to MgS without severe passivation of the Mg metal electrode surface.

Efficient photoelectrochemical water splitting with ultrathin films of hematite on three-dimensional nanophotonic structures.

Photoelectrochemical (PEC) solar water splitting represents a clean and sustainable approach for hydrogen (H2) production and substantial research are being performed to improve the conversion efficiency. Hematite (α-Fe2O3) is considered as a promising candidate for PEC water splitting due to its chemical stability, appropriate band structure, and abundance. However, PEC performance based on hematite is hindered by the short hole diffusion length that put a constraint on the active layer thickness and its light absorption capability. In this work, we have designed and fabricated novel PEC device structure with ultrathin hematite film deposited on three-dimensional nanophotonic structure. In this fashion, the nanophotonic structures can largely improve the light absorption in the ultrathin active materials. In addition, they also provide large surface area to accommodate the slow surface water oxidation process. As the result, high current density of 3.05 mA cm(-2) at 1.23 V with respect to the reversible hydrogen electrode (RHE) has been achieved on such nanophotonic structure, which is about three times of that for a planar photoelectrode. More importantly, our systematic analysis with experiments and modeling revealed that the design of high performance PEC devices needs to consider not only total optical absorption, but also the absorption profile in the active material, in addition to electrode surface area and carrier collection.

High-rate, ultralong cycle-life lithium/sulfur batteries enabled by nitrogen-doped graphene.

Nitrogen-doped graphene (NG) is a promising conductive matrix material for fabricating high-performance Li/S batteries. Here we report a simple, low-cost, and scalable method to prepare an additive-free nanocomposite cathode in which sulfur nanoparticles are wrapped inside the NG sheets (S@NG). We show that the Li/S@NG can deliver high specific discharge capacities at high rates, that is, ∼ 1167 mAh g(-1) at 0.2 C, ∼ 1058 mAh g(-1) at 0.5 C, ∼ 971 mAh g(-1) at 1 C, ∼ 802 mAh g(-1) at 2 C, and ∼ 606 mAh g(-1) at 5 C. The cells also demonstrate an ultralong cycle life exceeding 2000 cycles and an extremely low capacity-decay rate (0.028% per cycle), which is among the best performance demonstrated so far for Li/S cells. Furthermore, the S@NG cathode can be cycled with an excellent Coulombic efficiency of above 97% after 2000 cycles. With a high active S content (60%) in the total electrode weight, the S@NG cathode could provide a specific energy that is competitive to the state-of-the-art Li-ion cells even after 2000 cycles. The X-ray spectroscopic analysis and ab initio calculation results indicate that the excellent performance can be attributed to the well-restored C-C lattice and the unique lithium polysulfide binding capability of the N functional groups in the NG sheets. The results indicate that the S@NG nanocomposite based Li/S cells have a great potential to replace the current Li-ion batteries.

Process-specified emission factors and characteristics of VOCs from the auto-repair painting industry.

Daily use of passenger vehicles leads to considerable emission of volatile organic compounds (VOCs), which are key precursors to the ground-level ozone pollution. While evaporative and tailpipe emission of VOCs from the passenger vehicles can be eliminated largely, or even completely, by electrification, VOCs emission from the use of coatings in auto-repair is unavoidable and has long been ignored. Here, we present for the first time, to the best of our knowledge, a comprehensive investigation on the emission factors and process-specified characteristics of VOCs from auto-repair painting, based on field measurements over 15 representative auto-repair workshops in the Pearl-River-Delta area, China. Replacement of solvent-borne coatings with water-borne counterparts, which was only achieved partially in the Basecoat step but not in the Putty, Primer and Clearcoat steps, could reduce the per automobile VOCs emission from 756.5 to 489.6 g and the per automobile ozone formation potential (OFP) from 2776.5 to 1666.4 g. Implementation of exhaust after-treatment led to a further reduction of the per automobile VOCs emission to 340.9 g, which is still ca. 42% higher than that from the state-of-art painting processes for the manufacture of passenger vehicles. According to the analysis of VOCs compositions, the Putty process was dominated by the emission of styrene, while Primer, Basecoat (solvent-borne) and Clearcoat steps were all characterized by the emission of n-butyl acetate and xylenes. By contrast, water-borne Basecoat step showed a prominent emission of n-amyl alcohol. Notably, for the full painting process to repair an automobile, n-butyl acetate emerged as the most abundant species in the VOCs emission, whereas xylenes contributed most significantly to the OFP. Scenario analysis suggested that reducing VOCs contents in the coatings, as well as improving the after-treatment efficiency, were highly potential solutions for effective reduction of VOCs emission from auto-repair. Our study contributes to an update of industrial inventories of VOCs emission, and may provide valuable insights for reducing VOCs emission and OFPs from the auto-repair industry.

Enhanced electrocatalytic biomass oxidation at low voltage by Ni2+-O-Pd interfaces.

Challenges in direct catalytic oxidation of biomass-derived aldehyde and alcohol into acid with high activity and selectivity hinder the widespread biomass application. Herein, we demonstrate that a Pd/Ni(OH)2 catalyst with abundant Ni2+-O-Pd interfaces allows electrooxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid with a selectivity near 100 % and 2, 5-furandicarboxylic acid yield of 97.3% at 0.6 volts (versus a reversible hydrogen electrode) in 1 M KOH electrolyte under ambient conditions. The rate-determining step of the intermediate oxidation of 5-hydroxymethyl-2-furancarboxylic acid is promoted by the increased OH species and low C-H activation energy barrier at Ni2+-O-Pd interfaces. Further, the Ni2+-O-Pd interfaces prevent the agglomeration of Pd nanoparticles during the reaction, greatly improving the stability of the catalyst. In this work, Pd/Ni(OH)2 catalyst can achieve 100% 5-hydroxymethylfurfural conversion and >90% 2, 5-furandicarboxylic acid selectivity in a flow-cell and work stably over 200 h under a fixed cell voltage of 0.85 V.