Closing the carbon and nitrogen cycles by electrochemical methods using renewable energy to convert abundant or harmful feedstocks into high-value C- or N-containing chemicals has the potential to transform the global energy landscape. However, efficient conversion avenues have to date been mostly realized for the independent reduction of CO2 or NO3-. The synthesis of more complex C-N compounds still suffers from low conversion efficiency due to the inability to find effective catalysts. To this end, here we present amorphous bismuth-tin oxide nanosheets, which effectively reduce the energy barrier of the catalytic reaction, facilitating efficient and highly selective urea production. With enhanced CO2 adsorption and activation on the catalyst, a C-N coupling pathway based on *CO2 rather than traditional *CO is realized. The optimized orbital symmetry of the C- (*CO2) and N-containing (*NO2) intermediates promotes a significant increase in the Faraday efficiency of urea production to an outstanding value of 78.36% at -0.4 V vs RHE. In parallel, the nitrogen and carbon selectivity for urea formation is also enhanced to 90.41% and 95.39%, respectively. The present results and insights provide a valuable reference for the further development of new catalysts for efficient synthesis of high-value C-N compounds from CO2.
Single-atom (SA) catalysts with nearly 100% atom utilization have been widely employed in electrolysis for decades, due to the outperforming catalytic activity and selectivity. However, most of the reported SA catalysts are fixed through the strong bonding between the dispersed single metallic atoms with nonmetallic atoms of the substrates, which greatly limits the controllable regulation of electrocatalytic activity of SA catalysts. In this work, Pt-Ni bonded Pt SA catalyst with adjustable electronic states was successfully constructed through a controllable electrochemical reduction on the coordination unsaturated amorphous Ni(OH)2 nanosheet arrays. Based on the X-ray absorption fine structure analysis and first-principles calculations, Pt SA was bonded with Ni sites of amorphous Ni(OH)2, rather than conventional O sites, resulting in negatively charged Ptδ-. In situ Raman spectroscopy revealed that the changed configuration and electronic states greatly enhanced absorbability for activated hydrogen atoms, which were the essential intermediate for alkaline hydrogen evolution reaction. The hydrogen spillover process was revealed from amorphous Ni(OH)2 that effectively cleave the H-O-H bond of H2O and produce H atom to the Pt SA sites, leading to a low overpotential of 48 mV in alkaline electrolyte at -1000 mA cm-2 mg-1Pt, evidently better than commercial Pt/C catalysts. This work provided new strategy for the controllable modulation of the local structure of SA catalysts and the systematic regulation of the electronic states.
According to the traditional nucleation theory, crystals in solution nucleate under thermal fluctuations with random crystal orientation. Thus, nanosheet arrays grown on a substrate always exhibit disordered arrangements, which impede mass transfer during catalysis. To overcome this limitation, here, we demonstrate stress-induced, oriented nucleation and growth of nanosheet arrays. A regularly self-growing parallel nanosheet array is realized on a curved growth substrate. During electrochemical oxygen production, the ordered array maintains a steady flow of liquids in the microchannels, suppressing the detrimental production of flow-blocking oxygen bubbles typical of randomly oriented nanosheet arrays. Controllable parallel arrays, fully covered fluffy-like ultrathin nanosheets, and amorphous disordered structures altogether enable full-scale design of hierarchical interfaces from the micro- to the atomic scale, significantly improving the otherwise sluggish kinetics of oxygen evolution toward industrial ultrafast production. Record-high ultrafast oxygen production of 135 L·min-1·m-2 with high working current of 4000 mA·cm-2 is steadily achieved at a competitively low cell voltage of 2.862 V. These results and related insights lay the basis for further developments in oriented nucleation and growth of crystals beyond classical nucleation approaches, with benefits for large-scale, industrial electrochemical processes as shown here for ultrafast oxygen production.
There is ever-growing research interest in nanomaterials because of the unique properties that emerge on the nanometer scale. While crystalline nanomaterials have received a surge of attention for exhibiting state-of-the-art properties in various fields, their amorphous counterparts have also attracted attention in recent years owing to their unique structural features that crystalline materials lack. In short, amorphous nanomaterials only have short-range order at the atomic scale, and their atomic packing lacks long-range periodic arrangement, in which the coordinatively unsaturated environment, isotropic atomic structure, and modulated electron state all contribute to their outstanding performance in various applications. Given their intriguing characteristics, we herein present a series of representative works to elaborate on the structural advantages of amorphous nanomaterials as well as their enhanced electrocatalytic, surface-enhanced Raman scattering (SERS), and mechanical properties, thereby elucidating the underlying structure-function relationship. We hope that this proposed relationship will be universally applicable, thus encouraging future work in the design of amorphous materials that show promising performance in a wide range of fields.
Although direct generation of high-value complex molecules and feedstock by coupling of ubiquitous small molecules such as CO2 and N2 holds great appeal as a potential alternative to current fossil-fuel technologies, suitable scalable and efficient catalysts to this end are not currently available as yet to be designed and developed. To this end, here we prepare and characterize SbxBi1-xOy clusters for direct urea synthesis from CO2 and N2 via C-N coupling. The introduction of Sb in the amorphous BiOx clusters changes the adsorption geometry of CO2 on the catalyst from O-connected to C-connected, creating the possibility for the formation of complex products such as urea. The modulated Bi(II) sites can effectively inject electrons into N2, promoting C-N coupling by advantageous modification of the symmetry for the frontier orbitals of CO2 and N2 involved in the rate-determining catalytic step. Compared with BiOx, SbxBi1-xOy clusters result in a lower reaction potential of only -0.3 V vs. RHE, an increased production yield of 307.97 µg h-1 mg-1cat, and a higher Faraday efficiency (10.9%), pointing to the present system as one of the best catalysts for urea synthesis in aqueous systems among those reported so far. Beyond the urea synthesis, the present results introduce and demonstrate unique strategies to modulate the electronic states of main group p-metals toward their use as effective catalysts for multistep electroreduction reactions requiring C-N coupling.
The electrochemical carbon dioxide reduction reaction (CO2 RR) to formate is of great interest in the field of electrochemical energy. Cu-based material is an appealing electrocatalyst for the CO2 RR. However, retaining Cu2+ under the high cathodic potential of CO2 RR remains a great challenge, leading to low electrocatalytic selectivity, activity, and stability. Herein, inspired by corrosion science, a sacrificial protection strategy to stabilize interfacial crystalline CuO through embedding of active amorphous SnO2 (c-CuO/a-SnO2 ) is reported, which greatly boosts the electrocatalytic sensitivity, activity, and stability for CO2 RR to formate. The as-made hybrid catalyst can achieve superior high selectivity for CO2 RR to formate with a remarkable Faradaic efficiency (FE) of 96.7%, and a superhigh current density of over 1 A cm-2 that far outperforms industrial benchmarks (FE > 90%, current density > 300 mA cm-2 ). In situ X-ray absorption spectroscopy (XAS) and X-ray diffractionexperimental and theoretical calculation results reveal that the broadened s-orbital in interfacial a-SnO2 offers the lower orbital for extra electrons than Cu2+ , which can effectively retain nearby Cu2+ , and the high active interface significantly lowers the energy barrier of the limited step (* CO2 â * HCOO) and enhances the selectivity and activity for CO2 RR to formate.
Amorphous materials are metastable solids with only short-range order at the atomic scale, which results from local intermolecular chemical bonding. The lack of long-range order typical of crystals endows amorphous nanomaterials with unconventional and intriguing structural features, such as isotropic atomic environments, abundant surface dangling bonds, highly unsaturated coordination, etc. Because of these features and the ensuing modulation in electronic properties, amorphous nanomaterials display potential for practical applications in different areas. Motivated by these elements, here we provide an overview of the unique structural features, the general synthetic methods, and the potential for applications covered by contemporary research in amorphous nanomaterials. Furthermore, we discussed the possible theoretical mechanism for amorphous nanomaterials, examining how the unique structural properties and electronic configurations contribute to their exceptional performance. In particular, the structural benefits of amorphous nanomaterials as well as their enhanced electrocatalytic, optical, and mechanical properties, thereby clarifying the structure-function relationships, are highlighted. Finally, a perspective on the preparation and utilization of amorphous nanomaterials to establish mature systems with a superior hierarchy for various applications is introduced, and an outlook for future challenges and opportunities at the frontiers of this rapidly advancing field is proposed.
Catalytic strategies based on main group metals are significantly less advanced than those of transition metal catalysis, leaving untapped areas of potentially fruitful research. We here demonstrate an effective approach for the modulation of Bi 6p energy levels during the construction of atomically dispersed clusters of amorphous BiOx . Bi oxidation state is proposed to strongly affects the nitrogen fixation activity, with the half-occupied pz orbitals of the Bi2+ ions being highly efficient toward electron injection into the inert N2 molecule. With sufficient catalytic sites to adsorb and activate N2 , the bonding between N2 and catalyst is able to be in situ identified. The catalyst shows an outstanding Faraday efficiency (≈30 %) and high yield (≈113â µg h-1 mg-1 cat ) in NH3 production, outperforming most of the existing catalysts in aqueous solution. These results lay the basis for developing the potential of p-block elements for catalysis of multi-electron reactions.
The theoretical capacity of a given electrode material is ultimately determined by the number of electrons transferred in each redox center. The design of multi-electron transfer processes could break through the limitation of one-electron transfer and multiply the total capacity but is difficult to achieve because multiple electron transfer processes are generally thermodynamically and kinetically more complex. Here, we report the discovery of two-electron transfer in monolayer Ni(OH)2 nanosheets, which contrasts with the traditional one-electron transfer found in multilayer materials. First-principles calculations predict that the first oxidation process Ni2+ â Ni3+ occurs easily, whereas the second electron transfer in Ni3+ â Ni4+ is strongly hindered in multilayer materials by both the interlayer hydrogen bonds and the domain H structure induced by the Jahn-Teller distortion of the Ni3+ (t2g6eg1)-centered octahedra. In contrast, the second electron transfer can easily occur in monolayers because all H atoms are fully exposed. Experimentally, the as-prepared monolayer is found to deliver an exceptional redox capacity of â¼576 mA h/g, nearly 2 times the theoretical capacity of one-electron processes. In situ experiments demonstrate that monolayer Ni(OH)2 can transfer two electrons and most Ni ions transform into Ni4+ during the charging process, whereas bulk Ni(OH)2 can only be transformed partially. Our work reveals a new redox reaction mechanism in atomically thin Ni(OH)2 nanosheets and suggests a promising path toward tuning the electron transfer numbers to multiply the capacity of the relevant energy storage materials.
Although oxygen vacancies (Ov s) play a critical role for many applications of metal oxides, a controllable synthetic strategy for anisotropic Ov s remains a great challenge. Here, a novel strategy is proposed to achieve the regional dual structure with anisotropic Ov s at both the surface and in the interior of TiO2 by constructing amorphous domains. The as-prepared black TiO2 with amorphous domains exhibits superior activity in degrading rhodamine B (RhB) solutions, which can instantly decompose RhB with just a shake. First-principle simulations reveal that subsurface Ov s in TiO2 are energetically favored, resulting in the formation of amorphous domains in the interior region via diffusion of surface-formed Ov s into the subsurface. The stable Ov -induced amorphous domains in TiO2 with enhanced catalytic performances provide a scalable strategy to practical Ov engineering in functional metal oxides.
In this paper, we report the construction of network-like platinum (Pt) nanosheets based on Pt/reduced graphite oxide (Pt/rGO) hybrids by delicately utilizing a calorific-effect-induced-fusion strategy. The tiny Pt species first catalyzed the H2-O2 combination reaction. The released heat triggered the combustion of the rGO substrate under the assistance of the Pt species catalysis, which induced the fusion of the tiny Pt species into a network-like nanosheet structure. The loading amount and dispersity of Pt on rGO are found to be crucial for the successful construction of network-like Pt nanosheets. The as-prepared products present excellent catalytic hydrogenation activity and superior stability towards unsaturated bonds such as olefins and nitrobenzene. The styrene can be completely converted into phenylethane within 60 min. The turnover frequency (TOF) value of network-like Pt nanosheets is as high as 158.14 h-1, which is three times higher than that of the home-made Pt nanoparticles and among the highest value of the support-free bimetallic catalysts ever reported under similar conditions. Furthermore, the well dispersibility and excellent aggregation resistance of the network-like structure endows the catalyst with excellent recyclability. The decline of conversion could be hardly identified after five times recycling experiments.
Although the preparation of carbon composites has made great progress, the construction of systems comprising uniformly dispersed carbon as a framework to link active constituents still remains a challenge. Herein, a hierarchical Fe2 O3 /C composite was synthesized in a one-step biotemplating route, where agarose was firstly reacted with Fe3+ and Ca2+ ions, which resulted in a competitive interaction between these ions and the hydroxy groups, then partly calcined to achieve the final product that consisted of α-Fe2 O3 nanoparticles embedded in highly dispersed carbon. The carbon within the composite acts as an efficient photoelectron transfer channel to improve conductivity during photocatalysis. The hierarchical Fe2 O3 /C composite exhibited a photodegradation rate constant (k) of 0.091â min-1 , more than four times that of α-Fe2 O3 (0.020â min-1 ).
Aggregation-induced emission (AIE) system has long been regarded as a promising substitute to overcome the aggregation-caused quenching in traditional luminescent liquid crystals, which could further enhance its efficiency and application. However, due to the intrinsic weak interaction between hybrid components, heterogeneous inorganic materials-induced AIE process was rarely reported. In this study, trace amounts of amorphous Ag2S microrods and an AIE-active liquid crystalline compound tetraphenylethylene-propylbenzene (TPE-PPE) were proposed to construct additional intense interaction to trigger AIE effect. The enhanced concentration of unsaturated Ag ions and excess positive charge on Ag2S surface promote a cation-π interaction with TPE-PPE, leading to a 36-fold increase in fluorescence, which is predominately high in luminescent liquid crystal system. To the best of our knowledge, this is the first report of the AIE process activated by cation-π interaction. This novel approach would provide guidance to fabricate high-luminescence meso phases for future luminescent display device.
The surface charge of dendrimers is one of the key factors that determine their use in nanomedicine. Generation 5 poly(amido amine) dendrimers (G5 PAMAM) encapsulating with fluorescein sodium were employed to study the method to tune surface charge. Firstly, the surface primary amines were reacted with maleic anhydride to introduce double bonds. Then, l-cysteine and cysteamine were conjugated to these double bonds via thiol-ene additions in water, respectively. The surface charges of modified G5 PAMAMs were successfully controlled by tuning the molar ratio of L-cysteine to cysteamine. The surface charges of the resulting modified G5 PAMAMs varied from -16.0â¯mV to -3.7â¯mV at physiological pH. In addition, they showed good compatibility with proteins and cells compared with G5 PAMAM. Modified G5 PAMAMs and fibrinogen could coexist in solution without generating noticeable aggregation, while G5 PAMAM induces significant aggregation, indicating these modifications can effectively reduce the interaction force between G5 PAMAM and proteins. Furthermore, modified G5 PAMAMs exhibited negligible hemolysis, while G5 PAMAM caused severe hemolysis. The cytotoxicity assay demonstrated that modified G5 PAMAMs exhibited very low cytotoxicity to both HUVEC cells and KB cells (>90% cell viability) at high concentrations up to 2â¯mg/mL. The cellular uptake of them was much less efficient compared with that of G5 PAMAM. Moreover, the intravenous injected modified G5 PAMAMs were excreted by kidney with a relatively little accumulation in liver, confirming their good biocompatibility in vivo. It is expected that the modified G5 PAMAMs could be an excellent candidate for contrast agent carriers in the future.
Contrast Media , Dendrimers , Human Umbilical Vein Endothelial Cells/metabolism , Materials Testing , Animals , Contrast Media/chemistry , Contrast Media/pharmacokinetics , Contrast Media/pharmacology , Dendrimers/chemistry , Dendrimers/pharmacokinetics , Dendrimers/pharmacology , Female , Human Umbilical Vein Endothelial Cells/cytology , Humans , Mice , Mice, Inbred ICR , Surface Properties
Biomimetic solid-state nanofluidic diodes have attracted extensive research interest due to the possible applications in various fields, such as biosensing, energy conversion, and nanofluidic circuits. However, contributions of exterior surface to the transmembrane ionic transport are often ignored, which can be a crucial factor for ion rectification behavior. Herein, a rational design of robust sandwich-structured nanofluidic diode is shown by creating opposite charges on the exterior surfaces of a nanoporous membrane using inorganic oxides with distinct isoelectric points. Potential-induced changes in ion concentration within the nanopores lead to a current rectification; the results are subsequently supported by a theoretical simulation. Except for providing surface charges, functional inorganic oxides used in this work are complementary electrochromic materials. Hence, the sandwich-structured nanofluidic diode is further developed into an electrochromic membrane exhibiting a visual color change in response to redox potentials. The results show that the surface-charge-governed ionic transport and the nanoporous structure facilitate the migration of Li+ ions, which in turn enhance the electrochromic performance. It is envisioned that this work will create new avenues to design and optimize nanofluidic diodes and electrochromic devices.
Many ion channels in the cell membrane are believed to function as gates that control the water and ion flow through the transitions between an inherent hydrophobic state and a stimuli-induced hydration state. The construction of nanofluidic gating systems with high gating efficiency and reversibility is inspired by this hydrophobic gating behavior. A kind of electrically actuated nanochannel is developed by integrating a polypyrrole (PPy) micro/nanoporous film doped with perfluorooctanesulfonate ions onto an anodic aluminum oxide nanoporous membrane. Stemming from the reversible wettability switch of the doped PPy film in response to the applied redox potentials, the nanochannels exhibit highly efficient and reversible gating behaviors. The optimized gating ratio is over 105 , which is an ultrahigh value when compared with that of the existing reversibly gated nanochannels with comparable pore diameters. Furthermore, the gating behavior of the electrically actuated nanochannels shows excellent repeatability and stability. Based on this highly efficient and reversible gating function, the electrically actuated nanochannels are further applied for drug delivery, which achieves the pulsatile release of two water-soluble drug models. The electrically actuated nanochannels may find potential applications in accurate and on-demand drug therapy.
