ABSTRACT
Pure titanium is widely used in clinical implants, but its bioinert properties (poor strength and mediocre effect on bone healing) limit its use under load-bearing conditions. Modeling on the structure of collagen fibrils and specific nanocrystal plane arrangement of hydroxyapatite in the natural bone, a new type of titanium (Ti) with a highly aligned fibrous-grained (FG) microstructure is constructed. The improved attributes of FG Ti include high strength (≈950 MPa), outstanding affinity to new bone growth, and tight bone-implant contact. The bone-mimicking fibrous grains induce an aligned surface topological structure conducive to forming close contact with osteoblasts and promotes the expression of osteogenic genes. Concurrently, the predominant Ti(0002) crystal plane of FG Ti induces the formation of hydrophilic anatase titanium oxide layers, which accelerate biomineralization. In conclusion, this bioinspired FG Ti not only proves to show mechanical and bone-regenerative improvements but it also provides a new strategy for the future design of metallic biomaterials.
Subject(s)
Biocompatible Materials , Titanium , Titanium/chemistry , Durapatite , Bone RegenerationABSTRACT
There is an urgent need for the development of high performance electrocatalysts for the CO2 reduction reaction (CO2RR) to address environmental issues such as global warming and achieve carbon neutral energy systems. In recent years, Cu-based electrocatalysts have attracted significant attention in this regard. The present review introduces fundamental aspects of the electrocatalytic CO2RR process together with a systematic examination of recent developments in Cu-based electrocatalysts for the electroreduction of CO2 to various high-value multicarbon products. Current challenges and future trends in the development of advanced Cu-based CO2RR electrocatalysts providing high activity and selectivity are also discussed.
ABSTRACT
Electrocatalytic NO reduction is regarded as an attractive strategy to degrade the NO contaminant into useful NH3 , but the lack of efficient and stable electrocatalysts to facilitate such multiple proton-coupled electron-transfer processes impedes its applications. Here, we report on developing amorphous B2.6 C supported on a TiO2 nanoarray on a Ti plate (a-B2.6 C@TiO2 /Ti) as an NH3 -producing nanocatalyst with appreciable activity and durability toward the NO electroreduction. It shows a yield of 3678.6â µg h-1 cm-2 and a FE of 87.6 %, superior to TiO2 /Ti (563.5â µg h-1 cm-2 , 42.6 %) and a-B2.6 C/Ti (2499.2â µg h-1 cm-2 , 85.6 %). An a-B2.6 C@TiO2 /Ti-based Zn-NO battery achieves a power density of 1.7â mW cm-2 with an NH3 yield of 1125â µg h-1 cm-2 . An in-depth understanding of catalytic mechanisms is gained by theoretical calculations.
ABSTRACT
Graphene-based structures have been widely reported as promising metal-free catalysts for nitrogen reduction reaction. To explain the reactivity origin, various structures have been proposed and debated, including defects, functional groups, and doped heteroatoms. This computational work demonstrates that these structures may evolve from one to another under electrochemical conditions, generating weakly coordinated carbons, which have been identified as the active sites for N2 adsorption and activation.
ABSTRACT
Electrochemical nitrogen reduction reaction (NRR) over nonprecious-metal and single-atom catalysts has received increasing attention as a sustainable strategy to synthesize ammonia. However, the atomic-scale regulation of such active sites for NRR catalysis remains challenging because of the large distance between them, which significantly weakens their cooperation. Herein, the utilization of regular surface cavities with unique microenvironment on graphitic carbon nitride as "subnano reactors" to precisely confine multiple Fe and Cu atoms for NRR electrocatalysis is reported. The synergy of Fe and Cu atoms in such confined subnano space provides significantly enhanced NRR performance, with nearly doubles ammonia yield and 54%-increased Faradic efficiency up to 34%, comparing with the single-metal counterparts. First principle simulation reveals this synergistic effect originates from the unique Fe-Cu coordination, which effectively modifies the N2 absorption, improves electron transfer, and offers extra redox couples for NRR. This work thus provides new strategies of manipulating catalysts active centers at the sub-nanometer scale.
ABSTRACT
The face-to-face contact of a vertical heterojunction is beneficial to charge interaction in photocatalysis. However, constructing a vertical heterojunction with uncompromised redox ability still remains a challenge. Herein, we report the successful synthesis of a WO3-TiO2 vertical heterojunction via establishing an internal electric field across the interface. Experimental investigation and computational simulations reveal that strong electric coupling occurs at the WO3-TiO2 interface forming an internal electric field. The internal electric field induces a Z-scheme charge-carrier transfer through the heterojunction under light irradiation, which leads to effective charge separation and maintains high reaction potentials of charge-carriers. The improved photocatalytic activity of the WO3-TiO2 heterojunction is proved by enhanced generation of reactive oxygen species and accelerated Escherichia coli (E. coli) disinfection. This study provides new insights into understanding and designing Z-scheme heterogeneous photocatalysts.
ABSTRACT
Biological ion channels have remarkable ion selectivity, permeability and rectification properties, but it is challenging to develop artificial analogues. Here, we report a metal-organic framework-based subnanochannel (MOFSNC) with heterogeneous structure and surface chemistry to achieve these properties. The asymmetrically structured MOFSNC can rapidly conduct K+, Na+ and Li+ in the subnanometre-to-nanometre channel direction, with conductivities up to three orders of magnitude higher than those of Ca2+ and Mg2+, equivalent to a mono/divalent ion selectivity of 103. Moreover, by varying the pH from 3 to 8 the ion selectivity can be tuned further by a factor of 102 to 104. Theoretical simulations indicate that ion-carboxyl interactions substantially reduce the energy barrier for monovalent cations to pass through the MOFSNC, and thus lead to ultrahigh ion selectivity. These findings suggest ways to develop ion selective devices for efficient ion separation, energy reservation and power generation.
Subject(s)
Metal-Organic Frameworks , Metals/chemistry , Nanostructures/chemistry , Cations, Monovalent , Electric Conductivity , HumansABSTRACT
Photoinduced charge carrier behavior is critical in determining photoelectrocatalytic activity. In this study, a unique layer-doped metal-free polymeric carbon nitride (C3 N4 ) photoanode is fabricated by using one-pot thermal vapor deposition. With this method, a photoanode consisting of a phosphorus-doped top layer, boron-doped middle layer, and pristine C3 N4 bottom layer, was formed as a result of the difference in thermal polymerization kinetics associated with the boron-containing H3 BO3 -melamine complex and the phosphorus-containing H3 PO4 -dicyandiamide complex. This layer-doping fabrication strategy effectively contributes to the formation of dual junctions that optimizing charge carrier behavior. The ternary-layer C3 N4 photoanode exhibits significantly enhanced photoelectrochemical water oxidation activity compared to pristine C3 N4 , with a record photocurrent density of 150±10â µA cm-2 at 1.23â V vs. RHE. This layer-doping strategy provides an effective means for design and fabrication of photoelectrodes for solar water oxidation.
ABSTRACT
Metallic transition metal dichalcogenides, such as tantalum disulfide (TaS2), have recently emerged as promising electrocatalysts for the hydrogen evolution reaction. This work reports an effective strategy to further tune their performance through interfacial engineering, including lattice mismatch and electron injection between electrocatalysts and the underlying substrates. A unique two-zone chemical vapor deposition technique has been developed, and 2D TaS2 has been successfully grown on four different substrates, including glassy carbon, carbon fibers, Mo foil, and Au foil, providing excellent platforms to study catalyst-substrate interactions. Among them, TaS2 on Au foil offers the best performance with lowest overpotential and smallest charge transfer resistance, due to a suitable lattice mismatch and charge injection between TaS2 and Au, as revealed by theoretical calculations and experimental measurements. This work highlights the key roles the substrate plays in the catalysis and demonstrates the validity of interfacial engineering in catalyst design.
ABSTRACT
Boron has been explored as p-block catalysts for nitrogen reduction reaction (NRR) by density functional theory. Unlike transition metals, on which the active centers need empty d orbitals to accept the lone-pair electrons of the nitrogen molecule, the sp3 hybrid orbital of the boron atom can form B-to-N π-back bonding. This results in the population of the N-N π* orbital and the concomitant decrease of the N-N bond order. We demonstrate that the catalytic activity of boron is highly correlated with the degree of charge transfer between the boron atom and the substrate. Among the 21 concept-catalysts, single boron atoms supported on graphene and substituted into h-MoS2 are identified as the most promising NRR catalysts, offering excellent energy efficiency and selectivity against hydrogen evolution reaction.
ABSTRACT
Transition metal molybdenum (Mo) exhibits a strong capacity to adsorb nitrogen (N2), but the Mo-N2 interaction is too strong and thus it is difficult for ammonia (NH3) to be released from the catalyst surface. Bonding with nonmetals with strong electronegativity is helpful to weaken the Mo-N2 interaction, while the effect of hydrogen termination on catalyst surfaces needs to be evaluated given that the hydrogen evolution reaction (HER) is a key side reaction. This computational work aims to explore α-molybdenum carbide (Mo2C, orthorhombic phase) as an electrochemical catalyst for the full nitrogen reduction reaction (NRR). Our density functional theory (DFT) calculations focus on a (100) surface and demonstrate that (i) surface molybdenum and carbon can be terminated by hydrogen via the Volmer step and (ii) the NRR can occur on H-terminated Mo2C(100) with an energy requirement of 1.0-1.4 eV, depending on H-coverage. Although C-Mo bonding can remarkably reduce difficulty in NH3 release from a Mo-site, H-terminals result in performance deterioration. These results provide new insights into the development of NRR catalysts.