Designing Advanced Catalysts for Energy Conversion Based on Urea Oxidation Reaction

Urea oxidation reaction (UOR) is the underlying reaction that determines the performance of modern urea‐based energy conversion technologies. These technologies include electrocatalytic and photoelectrochemical urea splitting for hydrogen production and direct urea fuel cells as power engines. They have demonstrated great potentials as alternatives to current water splitting and hydrogen fuel cell systems with more favorable operating conditions and cost effectiveness. At the moment, UOR performance is mainly limited by the 6‐electron transfer process. In this case, various material design and synthesis strategies have recently been reported to produce highly efficient UOR catalysts. The performance of these advanced catalysts is optimized by the modification of their structural and chemical properties, including porosity development, heterostructure construction, defect engineering, surface functionalization, and electronic structure modulation. Considering the rich progress in this field, the recent advances in the design and synthesis of UOR catalysts for urea electrolysis, photoelectrochemical urea splitting, and direct urea fuel cells are reviewed here. Particular attention is paid to those design concepts, which specifically target the characteristics of urea molecules. Moreover, challenges and prospects for the future development of urea‐based energy conversion technologies and corresponding catalysts are also discussed.     

Construction of Nitrogen-Doped Biphasic Transition-Metal Sulfide Nanosheet Electrode for Energy-Efficient Hydrogen Production via Urea Electrolysis

Urea-assisted hybrid water splitting is a promising technology for hydrogen (H₂) production, but the lack of cost-effective electrocatalysts hinders its extensive application. Herein, it is reported that Nitrogen-doped Co₉S₈/Ni₃S₂ hybrid nanosheet arrays on nickel foam (N-Co₉S₈/Ni₃S₂/NF) can act as an active and robust bifunctional catalyst for both urea oxidation reaction (UOR) and hydrogen evolution reaction (HER), which could drive an ultrahigh current density of 400 mA cm⁻² at a low working potential of 1.47 V versus RHE for UOR, and gives a low overpotential of 111 mV to reach 10 mA cm⁻² toward HER. Further, a hybrid water electrolysis cell utilizing the synthesized N-Co₉S₈/Ni₃S₂/NF electrode as both the cathode and anode displays a low cell voltage of 1.40 V to reach 10 mA cm⁻², which can be powered by an AA battery with a nominal voltage of 1.5 V. The density functional theory (DFT) calculations decipher that N-doped heterointerfaces can synergistically optimize Gibbs free energy of hydrogen and urea, thus accelerating the catalytic kinetics of HER and UOR. This work significantly advances the development of the promising cobalt–nickel-based sulfide as a bifunctional electrocatalyst for energy-saving electrolytic H₂ production and urea-rich innocent wastewater treatment.     

A 2D Titanium Carbide MXene Flexible Electrode for High-Efficiency Light-Emitting Diodes

Although several transparent conducting materials such as carbon nanotubes, graphene, and conducting polymers have been intensively explored as flexible electrodes in optoelectronic devices, their insufficient electrical conductivity, low work function, and complicated electrode fabrication processes have limited their practical use. Herein, a 2D titanium carbide (Ti₃C₂) MXene film with transparent conducting electrode (TCE) properties, including high electrical conductivity (≈11 670 S cm⁻¹) and high work function (≈5.1 eV), which are achieved by combining a simple solution processing with modulation of surface composition, is described. A chemical neutralization strategy of a conducting-polymer hole-injection layer is used to prevent detrimental surface oxidation and resulting degradation of the electrode film. Use of the MXene electrode in an organic light-emitting diode leads to a current efficiency of ≈102.0 cd A⁻¹ and an external quantum efficiency of ≈28.5% ph/el, which agree well with the theoretical maximum values from optical simulations. The results demonstrate the strong potential of MXene as a solution-processable electrode in optoelectronic devices and provide a guideline for use of MXenes as TCEs in low-cost flexible optoelectronic devices.     

Nickel-Doped Carbon Dots as an Efficient and Stable Electrocatalyst for Urea Oxidation

Urea is a typical contaminant present in wastewater which may cause severe environmental problems. Electrochemical catalytic oxidation of urea has emerged as an efficient approach to solve this problem. Nevertheless, the current nickel-based catalysts (e.g., nickel hydroxide/sulfides) feature a high metal content. It not only lowers the utilization efficiency of nickel but also causes secondary pollution to the environment. Here, nickel-doped carbon dots (Ni-CDs) with an excellent and stable catalytic activity for the electrocatalytic urea oxidation reaction (UOR) are reported. Specifically, carbon dots (CDs) with abundant functional groups are synthesized by a one-pot hydrothermal method and then Ni-CDs with a very low metal content (1.1 at%) are prepared. The Ni²⁺ sites by coordination with carboxylic groups on the CDs provide excellent electrocatalytic activity and excellent durability for the UOR, as demonstrated by an anodic current density of 100 mA cm⁻² at a potential of 1.38 V (vs RHE) and similar experimental results in practical application. To the best of knowledge, this is the first report of CDs-based materials applied for the UOR, which opens an important new area of applicability for CDs as well as broadens the scope of the materials for electrochemical catalysis of urea.     

Phase-Inversion Induced 3D Electrode for Direct Acidic Electroreduction CO2 to Formic acid

Direct electrochemical CO₂ reduction to formic acid (FA) instead of formate is a challenging task due to the high acidity of FA and competitive hydrogen evolution reaction. Herein, 3D porous electrode (TDPE) is prepared by a simple phase inversion method, which can electrochemically reduce CO₂ to FA in acidic conditions. Owing to interconnected channels, high porosity, and appropriate wettability, TDPE not only improves mass transport, but also realizes pH gradient to build higher local pH micro-environment under acidic conditions for CO₂ reduction compared with planar electrode and gas diffusion electrode. Kinetic isotopic effect experiments demonstrate that the proton transfer becomes the rate-determining step at the pH of 1.8; however, not significant in neutral solution, suggesting that the proton is aiding the overall kinetics. Maximum FA Faradaic efficiency of 89.2% has been reached at pH 2.7 in a flow cell, generating FA concentration of 0.1 m . Integrating catalyst and gas–liquid partition layer into a single electrode structure by phase inversion method paves a facile avenue for direct production of FA by electrochemical CO₂ reduction.     

Understanding Fundamentals and Reaction Mechanisms of Electrode Materials for Na‐Ion Batteries

Development of efficient, affordable, and sustainable energy storage technologies has become an area of interest due to the worsening environmental issues and rising technological dependence on Li‐ion batteries. Na‐ion batteries (NIBs) have been receiving intensive research efforts during the last few years. Owing to their potentially low cost and relatively high energy density, NIBs are promising energy storage devices, especially for stationary applications. A fundamental understanding of electrode properties during electrochemical reactions is important for the development of low cost, high‐energy density, and long shelf life NIBs. This Review aims to summarize and discuss reaction mechanisms of the major types of NIB electrode materials reported. By appreciating how the material works and the fundamental flaws it possesses, it is hoped that this Review will assist readers in coming up with innovative solutions for designing better materials for NIBs.     

3D Carbon/Cobalt‐Nickel Mixed‐Oxide Hybrid Nanostructured Arrays for Asymmetric Supercapacitors

The electrochemical performance of supercapacitors relies not only on the exploitation of high‐capacity active materials, but also on the rational design of superior electrode architectures. Herein, a novel supercapacitor electrode comprising 3D hierarchical mixed‐oxide nanostructured arrays (NAs) of C/CoNi₃O₄ is reported. The network‐like C/CoNi₃O₄ NAs exhibit a relatively high specific surface area; it is fabricated from ultra‐robust Co‐Ni hydroxide carbonate precursors through glucose‐coating and calcination processes. Thanks to their interconnected three‐dimensionally arrayed architecture and mesoporous nature, the C/CoNi₃O₄ NA electrode exhibits a large specific capacitance of 1299 F/g and a superior rate performance, demonstrating 78% capacity retention even when the discharge current jumps by 100 times. An optimized asymmetric supercapacitor with the C/CoNi₃O₄ NAs as the positive electrode is fabricated. This asymmetric supercapacitor can reversibly cycle at a high potential of 1.8 V, showing excellent cycling durability and also enabling a remarkable power density of ～13 kW/kg with a high energy density of ～19.2 W·h/kg. Two such supercapacitors linked in series can simultaneously power four distinct light‐emitting diode indicators; they can also drive the motor of remote‐controlled model planes. This work not only presents the potential of C/CoNi₃O₄ NAs in thin‐film supercapacitor applications, but it also demonstrates the superiority of electrodes with such a 3D hierarchical architecture.     

Graphdiyne‐Supported NiCo2S4 Nanowires: A Highly Active and Stable 3D Bifunctional Electrode Material

The oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and overall water splitting are major energy and chemical conversion efforts. Progress in electrocatalytic reactions have shown that the future is limitless in many fields. However, it is urgent to develop efficient electrocatalysts. Here, the first graphdiyne‐supported efficient and bifunctional electrocatalyst is reported using 3D graphdiyne foam as scaffolds, and NiCo₂S₄ nanowires as building blocks (NiCo₂S₄ NW/GDF). NiCo₂S₄ NW/GDF exhibits outstanding catalytic activity and stability toward both OER and HER, as well as overall water splitting in alkaline media. Remarkably, it enables a high‐performance alkaline water electrolyzer with 10 and 20 mA cm^?2 at very low cell voltages of 1.53 and 1.56 V, respectively, and remarkable stability over 140 h of continuous electrolysis operation at 20 mA cm^?2. The results indicate that this catalyst has a bifunction that overcomes all reported bifunctional, nonprecious‐metal‐based ones.     

Synergism of Geometric Construction and Electronic Regulation: 3D Se‐(NiCo)Sx/(OH)x Nanosheets for Highly Efficient Overall Water Splitting

The exploration of highly efficient electrocatalysts for both oxygen and hydrogen generation via water splitting is receiving considerable attention in recent decades. Up till now, Pt‐based catalysts still exhibit the best hydrogen evolution reaction (HER) performance and Ir/Ru‐based oxides are identified as the benchmark for oxygen evolution reaction (OER). However, the high cost and rarity of these materials extremely hinder their large‐scale applications. This paper describes the construction of the ultrathin defect‐enriched 3D Se‐(NiCo)S_x/(OH)_x nanosheets for overall water splitting through a facile Se‐induced hydrothermal treatment. Via Se‐induced fabrication, highly efficient Se‐(NiCo)S_x/(OH)_x nanosheets are successfully fabricated through morphology optimization, defect engineering, and electronic structure tailoring. The as‐prepared hybrids exhibit relatively low overpotentials of 155 and 103 mV at the current density of 10 mA cm^?2 for OER and HER, respectively. Moreover, an overall water‐splitting device delivers a current density of 10 mA cm^?2 for ≈66 h without obvious degradation.     

Stereolithographic 3D Printing of Ceramics: Challenges and Opportunities for Structural Integrity

This article reviews the current activities at the Montanuniversität Leoben on the design, processing, and characterization of 3D printed advanced ceramics using the lithography-based manufacturing technology. An overview of the challenges and the opportunities offered to improve the mechanical properties of printing ceramics is given. Their brittle failure is analyzed within the framework of linear elastic fracture mechanics, considering specific aspects of additive manufacturing. Several issues associated with the printing process are addressed, such as surface quality, geometry control, influence of printing directions, as well as the need to establish testing protocols for 3D printed parts. Based on the layer-by-layer capabilities of the stereolithographic process, bio-inspired material design concepts are discussed aiming to enhance the mechanical resistance of 3D-printed ceramics. By tailoring the layer architecture and microstructure of the parts, high strength and fracture resistance may be achieved.     

Small-sized tungsten nitride anchoring into a 3D CNT-rGO framework as a superior bifunctional catalyst for the methanol oxidation and oxygen reduction reactions

The application of direct methanol fuel cells (DMFC) is hampered by high cost, low activity, and poor CO tolerance by the Pt catalyst. Herein, we designed a fancy 3D hybrid by anchoring tungsten nitride (WN) nanoparticles (NPs), of about 3 nm in size, into a 3D carbon nanotube-reduced graphene oxide framework (CNT-rGO) using an assembly route. After depositing Pt, the contacted and strongly coupled Pt–WN NPs were formed, resulting in electron transfer from Pt to WN. The 3D Pt–WN/CNT-rGO hybrid can be used as a bifunctional electrocatalyst for both methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR). In MOR, the catalysts showed excellent CO tolerance and a high mass activity of 702.4 mA·mg_Pt ^–1, 2.44 and 3.81 times higher than those of Pt/CNT-rGO and Pt/C(JM) catalysts, respectively. The catalyst also exhibited a more positive onset potential (1.03 V), higher mass activity (151.3 mA·mg_Pt ^–1), and better cyclic stability and tolerance in MOR than ORR. The catalyst mainly exhibited a 4e-transfer mechanism with a low peroxide yield. The high activity was closely related to hybrid structure. That is, the 3D framework provided a favorable path for mass-transfer, the CNT-rGO support was favorable for charge transfer, and strongly coupled Pt–WN can enhance the catalytic activity and CO-tolerance of Pt. Pt–WN/CNT-rGO represents a new 3D catalytic platform that is promising as an electrocatalyst for DMFC because it can catalyze both ORR and MOR in an acidic medium with good stability and highly efficient Pt utilization.

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Recent Advances in 3D Graphene Architectures and Their Composites for Energy Storage Applications

Graphene is widely applied as an electrode material in energy storage fields. However, the strong π–π interaction between graphene layers and the stacking issues lead to a great loss of electrochemically active surface area, damaging the performance of graphene electrodes. Developing 3D graphene architectures that are constructed of graphene sheet subunits is an effective strategy to solve this problem. The graphene architectures can be directly utilized as binder‐free electrodes for energy storage devices. Furthermore, they can be used as a matrix to support active materials and further improve their electrochemical performance. Here, recent advances in synthesizing 3D graphene architectures and their composites as well as their application in different energy storage devices, including various battery systems and supercapacitors are reviewed. In addition, their challenges for application at the current stage are discussed and future development prospects are indicated.     

Iterative solvers for 3D linear and nonlinear elasticity problems: Displacement and mixed formulations

We present new iterative solvers for large‐scale linear algebraic systems arising from the finite element discretization of the elasticity equations. We focus on the numerical solution of 3D elasticity problems discretized by quadratic tetrahedral finite elements and we show that second‐order accuracy can be obtained at very small overcost with respect to first‐order (linear) elements. Different Krylov subspace methods are tested on various meshes including elements with small aspect ratio. We first construct a hierarchical preconditioner for the displacement formulation specifically designed for quadratic discretizations. We then develop efficient tools for preconditioning the 2 × 2 block symmetric indefinite linear system arising from mixed (displacement‐pressure) formulations. Finally, we present some numerical results to illustrate the potential of the proposed methods. Copyright © 2010 John Wiley & Sons, Ltd.     

Zirconium‐Regulation‐Induced Bifunctionality in 3D Cobalt–Iron Oxide Nanosheets for Overall Water Splitting

The design of high‐efficiency non‐noble bifunctional electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is paramount for water splitting technologies and associated renewable energy systems. Spinel‐structured oxides with rich redox properties can serve as alternative low‐cost OER electrocatalysts but with poor HER performance. Here, zirconium regulation in 3D CoFe₂O₄ (CoFeZr oxides) nanosheets on nickel foam, as a novel strategy inducing bifunctionality toward OER and HER for overall water splitting, is reported. It is found that the incorporation of Zr into CoFe₂O₄ can tune the nanosheet morphology and electronic structure around the Co and Fe sites for optimizing adsorption energies, thus effectively enhancing the intrinsic activity of active sites. The as‐synthesized 3D CoFeZr oxide nanosheet exhibits high OER activity with small overpotential, low Tafel slope, and good stability. Moreover, it shows unprecedented HER activity with a small overpotential of 104 mV at 10 mA cm^?2 in alkaline media, which is better than ever reported counterparts. When employing the CoFeZr oxides nanosheets as both anode and cathode catalysts for overall water splitting, a current density of 10 mA cm^?2 is achieved at the cell voltage of 1.63 V in 1.0 m KOH.     

Confine,Defect, and Interface Manipulation of Fe3Se4/3D Graphene Targeting Fast and Stable Potassium-Ion Storage

The fast electrochemical kinetics behavior and long cycling life have been the goals in developing anode materials for potassium ion batteries (PIBs). On account of high electron conductivity and theoretical capacity, transition metal selenides have been deemed as one of the promising anode materials for PIBs. Herein, a systematic structural manipulation strategy, pertaining to the confine of Fe₃Se₄ particles by 3D graphene and the dual phosphorus (P) doping to the Fe₃Se₄/3DG (DP-Fe₃Se₄/3DG), has been proposed to fulfill the efficient potassium-ion (K-ion) evolution kinetics and thus boost the K-ion storage performance. The theoretical calculation results demonstrate that the well-designed dual P doping interface can effectively promote K-ion adsorption behavior and provide a low energy barrier for K-ion diffusion. The insertion-conversion and adsorption mechanism for multi potassium storage behavior in DP-Fe₃Se₄/3DG composite has been also deciphered by combining the in situ/ex situ X-ray diffraction and operando Raman spectra evidences. As expected, the DP-Fe₃Se₄/3DG anode exhibits superior rate capability (120.2 mA h g⁻¹ at 10 A g⁻¹) and outstanding cycling performance (157.9 mA h g⁻¹ after 1000 cycles at 5 A g⁻¹).     

3D Mimicry of Native‐Tissue‐Fiber Architecture Guides Tendon‐Derived Cells and Adipose Stem Cells into Artificial Tendon Constructs

Tendon and ligament (T/L) function is intrinsically related with their unique hierarchically and anisotropically organized extracellular matrix. Their natural healing capacity is, however, limited. Here, continuous and aligned electrospun nanofiber threads (CANT) based on synthetic/natural polymer blends mechanically reinforced with cellulose nanocrystals are produced to replicate the nanoscale collagen fibrils grouped into microscale collagen fibers that compose the native T/L. CANT are then incrementally assembled into 3D hierarchical scaffolds, resulting in woven constructions, which simultaneously mimic T/L nano‐to‐macro architecture, nanotopography, and nonlinear biomechanical behavior. Biological performance is assessed using human‐tendon‐derived cells (hTDCs) and human adipose stem cells (hASCs). Scaffolds nanotopography and microstructure induce a high cytoskeleton elongation and anisotropic organization typical of tendon tissues. Moreover, the expression of tendon‐related markers (Collagen types I and III, Tenascin‐C, and Scleraxis) by both cell types, and the similarities observed on their expression patterns over time suggest that the developed scaffolds not only prevent the phenotypic drift of hTDCs, but also trigger tenogenic differentiation of hASCs. Overall, these results demonstrate a feasible approach for the scalable production of 3D hierarchical scaffolds that exhibit key structural and biomechanical properties, which can be advantageously explored in acellular and cellular T/L TE strategies.