Thermo-photo catalytic anode process for carbonate-superstructured solid fuel cells.

Converting hydrocarbons and greenhouse gases (i.e., carbon dioxide, CO2) directly into electricity through fuel cells at intermediate temperatures (450 to 550 °C) remains a significant challenge, primarily due to the sluggish activation of C-H and C=O bonds. Here, we demonstrated a unique strategy to address this issue, in which light illumination was introduced into the thermal catalytic CO2 reforming of ethane in the anode as a unique thermo-photo anode process for carbonate-superstructured solid fuel cells. The light-enhanced fuel activation led to excellent cell performance with a record-high peak power density of 168 mW cm-2 at an intermediate temperature of 550 °C. Furthermore, no degradation was observed during ~50 h operation. Such a successful integration of photo energy into the fuel cell system provides a new direction for the development of efficient fuel cells.

Superstructured NiMoO4@CoMoO4 core-shell nanofibers for supercapacitors with ultrahigh areal capacitance.

High areal capacitance for a practical supercapacitor electrode requires both large mass loading and high utilization efficiency of electroactive materials, which presents a great challenge. Herein, we demonstrated the unprecedented synthesis of superstructured NiMoO4@CoMoO4 core-shell nanofiber arrays (NFAs) on a Mo-transition-layer-modified nickel foam (NF) current collector as a new material, achieving the synergistic combination of highly conductive CoMoO4 and electrochemical active NiMoO4. Moreover, this superstructured material exhibited a large gravimetric capacitance of 1,282.2 F/g in 2 M KOH with a mass loading of 7.8 mg/cm2, leading to an ultrahigh areal capacitance of 10.0 F/cm2 that is larger than any reported values of CoMoO4 and NiMoO4 electrodes. This work provides a strategic insight for rational design of electrodes with high areal capacitances for supercapacitors.

Carbonate-superstructured solid fuel cells with hydrocarbon fuels.

A basic requirement for solid oxide fuel cells (SOFCs) is the sintering of electrolyte into a dense impermeable membrane to prevent the mixing of fuel and oxygen for a sufficiently high open-circuit voltage (OCV). However, herein, we demonstrate a different type of fuel cell, a carbonate-superstructured solid fuel cell (CSSFC), in which in situ generation of superstructured carbonate in the porous samarium-doped ceria layer creates a unique electrolyte with ultrahigh ionic conductivity of 0.17 S⋅cm-1 at 550 °C. The CSSFC achieves unprecedented high OCVs (1.051 V at 500 °C and 1.041 V at 550 °C) with methane fuel. Furthermore, the CSSFC exhibits a high peak power density of 215 mW⋅cm-2 with dry methane fuel at 550 °C, which is higher than all reported values of electrolyte-supported SOFCs. This provides a different approach for the development of efficient solid fuel cells.

Gradient Functional Layer Anode for Carbonate-Superstructured Solid Fuel Cells with Ethane Fuel.

Carbonate-superstructured solid fuel cells (CSSFCs) are an emerging type of fuel cells with high flexibility of fuels. However, using ethane fuel for solid fuel cells is a great challenge due to serious degradation of their anodes. Herein, this critical issue is solved by creating a novel gradient functional layer anode for CSSFCs. First, a finer-scale anode with a larger surface area is demonstrated to provide more active sites for the internal reforming reaction of ethane, achieving a 60% higher ethane conversion rate and 40% lower polarization resistance than conventional anodes. Second, incorporating a gradient functional layer into the anode results in an additional 50% enhancement in the peak power density of CSSFCs to a record high value (up to 241 mW cm-2) with dry ethane fuel at a low temperature of 550 °C, which is even comparable to the power density of conventional solid oxide fuel cells above 700 °C. Furthermore, the CSSFC with the gradient anode exhibits excellent durability for over 200 h. This finding provides a new strategy to develop efficient anodes for hydrocarbon fuels.

Thermo-photo catalysis: a whole greater than the sum of its parts.

Thermo-photo catalysis, which is the catalysis with the participation of both thermal and photo energies, not only reduces the large energy consumption of thermal catalysis but also addresses the low efficiency of photocatalysis. As a whole greater than the sum of its parts, thermo-photo catalysis has been proven as an effective and promising technology to drive chemical reactions. In this review, we first clarify the definition (beyond photo-thermal catalysis and plasmonic catalysis), classification, and principles of thermo-photo catalysis and then reveal its superiority over individual thermal catalysis and photocatalysis. After elucidating the design principles and strategies toward highly efficient thermo-photo catalytic systems, an ample discussion on the synergetic effects of thermal and photo energies is provided from two perspectives, namely, the promotion of photocatalysis by thermal energy and the promotion of thermal catalysis by photo energy. Subsequently, state-of-the-art techniques applied to explore thermo-photo catalytic mechanisms are reviewed, followed by a summary on the broad applications of thermo-photo catalysis and its energy management toward industrialization. In the end, current challenges and potential research directions related to thermo-photo catalysis are outlined.

Mesoporous MgO enriched in Lewis base sites as effective catalysts for efficient CO2 capture.

Capturing CO2 has become increasingly important. However, wide industrial applications of conventional CO2 capture technologies are limited by their slow CO2 sorption and desorption kinetics. Accordingly, this research is designed to overcome the challenge by synthesizing mesoporous MgO nanoparticles (MgO-NPs) with a new method that uses PEG 1500 as a soft template. MgO surface structure is nonstoichiometric due to its distinctive shape; the abundant Lewis base sites provided by oxygen vacancies promote CO2 capture. Adding 2 wt % MgO-NPs to 20 wt % monoethanolamine (MEA) can increase the breakthrough time (the time with 90% CO2 capturing efficiency) by ∼3000% and can increase the CO2 absorption capacity within the breakthrough time by ∼3660%. The data suggest that MgO-NPs can accelerate the rate and increase CO2 desorption capacity by up to ∼8740% and ∼2290% at 90 °C, respectively. Also, the excellent stability of the system within 50 cycles is verified. These findings demonstrate a new strategy to innovate MEA absorbents currently widely used in commercial post-combustion CO2 capture plants.

3D Graphene Materials: From Understanding to Design and Synthesis Control.

Carbon materials, with their diverse allotropes, have played significant roles in our daily life and the development of material science. Following 0D C60 and 1D carbon nanotube, 2D graphene materials, with their distinctively fascinating properties, have been receiving tremendous attention since 2004. To fulfill the efficient utilization of 2D graphene sheets in applications such as energy storage and conversion, electrochemical catalysis, and environmental remediation, 3D structures constructed by graphene sheets have been attempted over the past decade, giving birth to a new generation of graphene materials called 3D graphene materials. This review starts with the definition, classifications, brief history, and basic synthesis chemistries of 3D graphene materials. Then a critical discussion on the design considerations of 3D graphene materials for diverse applications is provided. Subsequently, after emphasizing the importance of normalized property characterization for the 3D structures, approaches for 3D graphene material synthesis from three major types of carbon sources (GO, hydrocarbons and inorganic carbon compounds) based on GO chemistry, hydrocarbon chemistry, and new alkali-metal chemistry, respectively, are comprehensively reviewed with a focus on their synthesis mechanisms, controllable aspects, and scalability. At last, current challenges and future perspectives for the development of 3D graphene materials are addressed.

Bifunctional electrocatalysts for oxygen reduction and oxygen evolution: a theoretical study on 2D metallic WO2-supported single atom (Fe, Co, or Ni) catalysts.

Catalysts play a critical role in the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) for energy storage, conversion, and utilization. Herein, first-principles density functional theory (DFT) calculations demonstrated that single-metal-atom (Fe, Co, or Ni) sites can bind to the surface of 2D WO2, enhancing the adsorption of intermediates involved in the OER/ORR. Furthermore, it was found that the single-metal-atom-doped 2D WO2 achieves the smallest OER and ORR overpotentials of 0.42 V and 0.40 V, respectively, which are comparable to those of IrO2 or Pt-based catalysts. This predicts the excellent OER/ORR catalytic activities of the single-metal-atom (Fe, Co, or Ni) doped 2D WO2, which would be a promising bifunctional catalyst for fuel cells, water splitting, and metal-air batteries.

Phosphorus-based metal-free Z-scheme 2D van der Waals heterostructures for visible-light photocatalytic water splitting: a first-principles study.

Direct splitting of water over semiconductors under sunlight irradiation would be a promising approach for hydrogen production and solar energy utilization. In this work, BlueP/PN with a 2D van der Waals (vdW) heterostructure is proposed as a novel catalyst for the Z-scheme photocatalytic system. Its electronic structures, optical properties, and combined configuration were systematically evaluated by hybrid density functional theory (DFT) calculations. It was revealed that the 2D vdW heterostructure of BlueP/PN can play an important role in water splitting under visible light irradiation. This predicts a novel design of P-based vdW heterostructures for efficient photocatalysts.

S-Vacancy induced indirect-to-direct band gap transition in multilayer MoS2.

Two-dimensional (2D) MoS2 has various potential applications due to its attractive band gap of 1.29-1.90 eV and unique photoelectric properties. Furthermore, it is well-known that multilayer and bulk MoS2 structures possess an indirect band gap. In this paper, however, our first-principles calculations demonstrated that the creation of S vacancies in the multilayer and bulk MoS2 structures can achieve indirect-to-direct band gap transition, leading to a decrease in the band gap energies from 0.984-1.542 eV to 0.629-0.971 eV. Although the generation of Mo vacancies cannot cause such indirect-to-direct band gap transition, the Mo vacancies also decrease the band gap energies of the multilayer and bulk MoS2 structures to 0.369-0.460 eV. Furthermore, the band gap energy of the vacancy-defected multilayer MoS2 decreases with the increasing number of layers. Optical properties are also remarkably affected by atomic vacancies, that is, the absorption edges in the defect structures of MoS2 present a redshift and significantly enhance the visible light absorption compared to the corresponding pristine structures. These findings provide a novel approach to tuning the electronic structure and dielectric properties of MoS2 for specific future applications.

Ultrafast, Low-Cost, and Mass Production of High-Quality Graphene.

Fast, mass, and low-cost production of high-quality graphene, which is alluring, remains a great challenge, even though some approaches have shown potential for mass synthesis of graphene. Very recently a great breakthrough was made by Tour and co-workers (Nature 2020, 577, 647-651): in just a second, easily exfoliated and highly crystalline graphene was produced from abundant carbon-containing species by cost-effective flash Joule heating with a low energy input of 7.2 kJ per gram graphene. Such an ultrafast, economic, and scalable process for high-quality graphene production can be considered as a milestone in the graphene field and is highlighted in this article.

Mo6S8-based single-metal-atom catalysts for direct methane to methanol conversion.

The single atom catalysts have been attracting much attention for catalysis. In this work, the significant influence of single-metal-atom (M = K, Ti, Fe, Co, Ni, Cu, Rh) doping on a Mo6S8 cluster was revealed for the direct methane to methanol conversion in water stream using density functional theory calculations. It was found that all single atom dopants help to facilitate the conversion via the steam reforming of methane (SRM). The single Fe atom on Mo6S8 (Fe-Mo6S8) exhibits the most significant promoting effect, which is followed by Ni, Co, Rh-Mo6S8 > K, Ti, Cu-Mo6S8 > Mo6S8 in a decreasing sequence. The enhanced activity by single atom doping on Mo6S8 is mainly associated with the interplay between the ensemble effect via the direct participation of an active M dopant and the site confinement imposed by doping of a single M atom, in tuning the methane conversion and methanol selectivity. It generates the new active center, M, which confines the SRM to occur at the M-Mo bridge sites and facilitates the selective production of methanol. A good single-atom promoter should not only bind *OH or *O moderately, being strongly enough to help water dissociation and weakly enough to allow the oxidation of methane, but also impose the confinement effect to facilitate the C-O bond association and production of methanol. Our results highlight the importance of the interplay among ligand, ensemble, and confinement effects in promoting the complex SRM over single atom catalysts.

Memristive Behavior and Ideal Memristor of 1T Phase MoS2 Nanosheets.

Memristor, which had been predicted a long time ago (Chua, L. O. IEEE Trans. Circuit Theory 1971, 18, 507), was recently invented (Strukov, D. B.; et al. Nature 2008, 453, 80). The introduction of a memristor is expected to open a new era for nonvolatile memory storage, neuromorphic computing, digital logic, and analog circuit. Furthermore, several breakthroughs were made for memristive phenomena and transistors with single-layer MoS2 (Sangwan, V. K.; et al. Nat. Nanotechnol. 2015, 10, 403. van der Zande, A. M.; et al. Nat. Mater. 2013, 12, 554. Liu, H.; et al. ACS Nano 2014, 8, 1031. Bessonov, A. A.; et al. Nat. Mater. 2015, 14, 199. Yuan, J.; et al. Nat. Nanotechnol. 2015, 10, 389). Herein, we demonstrate that 2H phase of bulk MoS2 possessed an ohmic feature, whereas 1T phase of exfoliated MoS2 nanosheets exhibited a unique memristive behavior due to voltage-dependent resistance change. Furthermore, an ideal odd-symmetric memristor with odd-symmetric I-V characteristics was successfully fabricated by the 1T phase MoS2 nanosheets via combining two asymmetric switches antiserially.

The Bright Future for Electrode Materials of Energy Devices: Highly Conductive Porous Na-Embedded Carbon.

High electrical conductivity and large accessible surface area, which are required for ideal electrode materials of energy conversion and storage devices, are opposed to each other in current materials. It is a long-term goal to solve this issue. Herein, we report highly conductive porous Na-embedded carbon (Na@C) nanowalls with large surface areas, which have been synthesized by an invented reaction of CO with liquid Na. Their electrical conductivities are 2 orders of magnitude larger than highly conductive 3D graphene. Furthermore, almost all their surface areas are accessible for electrolyte ions. These unique properties make them ideal electrode materials for energy devices, which significantly surpass expensive Pt. Consequently, the dye-sensitized solar cells (DSSCs) with the Na@C counter electrode has reached a high power conversion efficiency of 11.03%. The Na@C also exhibited excellent performance for supercapacitors, leading to high capacitance of 145 F g-1 at current density of 1 A g-1.

Emerging approaches of utilizing trees to produce advanced structural and functional materials.

The global number of trees is approximately 3 trillion, covering 31% of the land area. Trees are considered a cheap, abundant, renewable, and environmentally friendly feedstock for producing advanced structural and functional materials toward a widespread application in sustainable energy and environment. In this highlight, we reveal the structure and composition of wood, leaves, and tree extracts, and then highlight the strategies to control their hierarchical structures and properties. Moreover, we provide an up-to-date overview of their emerging applications in sustainable buildings, ionic nanofluidics, batteries, capacitors, solar cells, environmental remediation, biodegradable packaging, and nanomaterial synthesis. Finally, we outline the challenges and opportunities in valorizing trees for creating a sustainable future.

Complete Degradation of Polyolefin Plastic Wastes to High-Value Products.

Plastic wastes continuously accumulate, causing critical environmental issues. It is urgent to develop efficient strategies to convert them to valuable products. Very recently, two novel approaches for plastic recycling were reported by Huber et al. (Science, 2023, 381, 660-666) and Liu et al. (Science, 2023, 381, 666-671), where polyethylene (PE) and polypropylene (PP) plastics were converted into potentially valuable products, such as alcohols, aldehydes, surfactants, and detergents. The two processes achieved complete degradation, high selectivity of target products, as well as high values of products, showing economic feasibility for industrial scale-up. These breakthroughs for plastic recycling are highlighted in this article.

Critical Role of In-Situ-Generated Eutectic Carbonates in Superstructured Solid Fuel Cells.

As a distinct type of fuel cell, a carbonate-superstructured solid fuel cell (CSSFC), which possesses excellent performance and easy fabrication as well as low cost, was recently invented by our group. Herein, we demonstrated the critical role of the in-situ-generated eutectic carbonate phase in CSSFC. Namely, the in-situ generation of eutectic Li2CO3/Na2CO3 system increased the oxygen ionic conductivity of Ce0.8Sm0.2O1.9 solid electrolyte by 20 times (from 3.5 × 10-3 to 7.3 × 10-2 S cm-1), leading to 6 times enhancement of CSSFC peak powder density (up to 206 mW cm-2) with methane fuel at 550 °C. This finding is extremely important for designing efficient CSSFCs.

Recent progress in removal of heavy metals from wastewater: A comprehensive review.

The heavy metal pollution constitutes a critical environmental issue. This has stimulated intensive efforts to develop treatment techniques for their removal from wastewater, including adsorption, membrane separation, precipitation/electrodeposition, ion exchange, coagulation-flocculation, flotation/electroflotation, solvent extraction, catalysis, and bioremediation. This article provides a comprehensive review on the advances in those techniques with the focus on the recent decade (2013-2023). It shows that the adsorption has attracted the most attention and membrane filtration the second, followed by precipitation and ion exchange. Interests in bioremediation and electrochemical treatments as well as catalysis are expected to increase in the future. Furthermore, the combination of different processes is a promising strategy to develop efficient hybrid technologies.

Chemical recycling of plastic wastes with alkaline earth metal oxides: A review.

Plastics have been widely used in daily life and industries due to their low cost and high durability, leading to huge production of plastics and tens of millions of plastic wastes every year. Chemical recycling can recycle contaminated and degraded plastics (that mechanical recycling cannot deal with) to obtain value-added products, which potentially solves the environmental problems caused by plastics and realizes a circular economy. Alkaline earth metal oxides, as a category of cost-effective and multi-functional materials, have been widely used in chemical recycling of common plastics, acting as three roles: catalyst, template, and absorbent. Among five commercial plastics, polyethylene terephthalate is suitable for pyrolysis and solvolysis. Polyethylene and polypropylene, which are ideal precursors for synthesis of carbon nanotubes, could be combined with biomass for co-pyrolysis. Polyvinyl chloride needs to be pretreated to reduce chloride content prior to pyrolysis. Depolymerization of polystyrene into monomers is attractive. This review summarized the chemical recycling approaches of commercial plastics and the strategies with alkaline earth metal oxides for the development of efficient recycling processes. It will aid understanding of the advances and challenges in the field and promote the future research.