Template Synthesis Research Articles

Turning natural copper phthalocyanine into high-loading single-atom catalysts using an electrochemically-generated template and cationic substitution

Phthalocyanine (PC) has a unique N4-coordinated structure that offers an inherent advantage with respect to the accommodation of metal ions. This feature can help overcome the limitations of many single-atom electrocatalysts, i.e. low loading and poor stability. Here, we detail the development of a universal electrochemical template and a cationic substitution synthesis protocol for preparing various single-atom catalysts with high-loading (≌ 8.6 wt%) from commercial copper phthalocyanine (CuPC). Commercial CuPC is transformed into Cu NPs and vacant N4-sites are created during applied potential cycling. The generated vacant N4-sites, with strong negative charges, can take-up Pd2+ ions from a precursor solution to create single-atom catalysts with Pd high-loadings. The material’s structural transformation and cationic substitution mechanism were investigated by in situ X-ray absorption spectroscopy (XAS). We also demonstrate the viability of extending the proposed electrochemical template synthesis method to the development of other high-loading transition metal single-atom catalysts, e.g., Ni, Co, and Fe.

Ionic liquid templated synthesis of cobalt‐substituted mesoporous aluminophosphates: A novel heterogeneous catalyst for selective oxidation of cyclohexane to cyclohexanol

AbstractOrdered hexagonal mesoporous aluminophosphate and its cobalt‐substituted analogue were successfully synthesized using ionic liquid as a structure‐directing agent. The resulting materials were systematically characterized by various analytical, spectroscopic, and imaging methods, confirming the presence of divalent cobalt in the tetrahedral framework of the matrix. Further, the high surface area, pore volume, and thicker mesopore walls of these materials impart good thermal and hydrothermal stability. The mesoporous catalysts showed excellent activity towards the oxidation of cyclohexane reactions using hydrogen peroxide as an oxidant, with 98.5 % conversion and 90.4 % selectivity towards cyclohexanol.

Retention of the RNA ends provides the molecular memory for maintaining the activation of the Csm complex.

The type III CRISPR-Cas effector complex Csm functions as a molecular Swiss army knife that provides multilevel defense against foreign nucleic acids. The coordinated action of three catalytic activities of the Csm complex enables simultaneous degradation of the invader's RNA transcripts, destruction of the template DNA and synthesis of signaling molecules (cyclic oligoadenylates cAn) that activate auxiliary proteins to reinforce CRISPR-Cas defense. Here, we employed single-molecule techniques to connect the kinetics of RNA binding, dissociation, and DNA hydrolysis by the Csm complex from Streptococcus thermophilus. Although single-stranded RNA is cleaved rapidly (within seconds), dual-color FCS experiments and single-molecule TIRF microscopy revealed that Csm remains bound to terminal RNA cleavage products with a half-life of over 1 hour while releasing the internal RNA fragments quickly. Using a continuous fluorescent DNA degradation assay, we observed that RNA-regulated single-stranded DNase activity decreases on a similar timescale. These findings suggest that after fast target RNA cleavage the terminal RNA cleavage products stay bound within the Csm complex, keeping the Cas10 subunit activated for DNA destruction. Additionally, we demonstrate that during Cas10 activation, the complex remains capable of RNA turnover, i.e. of ongoing degradation of target RNA.

Boric acid templating synthesis of highly-dense yet ultramicroporous carbons for compact capacitive energy storage

Carbon-based supercapacitors have shown great promise for miniaturized electronics and electric vehicles, but are usually limited by their low volumetric performance, which is largely due to the inefficient utilization of carbon pores in charge storage. Herein, we develop a reliable and scalable boric acid templating technique to prepare boron and oxygen co-modified highly-dense yet ultramicroporous carbons (BUMCs). The carbons are featured with high density (up to 1.62 g cm−3), large specific surface area (up to 1050 m2 g−1), narrow pore distribution (0.4–0.6 nm) and exquisite pore surface functionalities (mainly –BC2O, −BCO2, and –COH groups). Consequently, the carbons show exceptionally compact capacitive energy storage. The optimal BUMC-0.5 delivers an outstanding volumetric capacitance of 431 F cm−3 and a high-rate capability in 1 M H2SO4. In particular, an ever-reported high volumetric energy density of 32.6 Wh L−1 can be harvested in an aqueous symmetric supercapacitor. Our results demonstrate that the –BC2O and –BCO2 groups on the ultramicropore walls can facilitate the internal SO42− ion transport, thus leading to an unprecedented high utilization efficiency of ultramicropores for charge storage. This work provides a new paradigm for construction and utilization of dense and ultramicroporous carbons for compact energy storage.

Nickel- and/or iron-based ceria-supported catalysts for CO oxidation in combustion exhaust gases

We present a series of Ni, Fe, and mixed NiFe-based catalysts, deposited onto ceria prepared with either soft templated (with CTAB) or hard templated (with SBA-15) syntheses. The prepared materials were thoroughly characterized with SEM, HRTEM, EDX, ICP-MS, PXRD, and N2 adsorption techniques, to fully comprehend their physicochemical properties. All catalysts were then tested for carbon monoxide oxidation reaction at different temperatures, aiming to reach temperature and feed composition conditions typical of combustion exhausts from industrial and power plants (350–400 °C, in the presence of competitive species such as CO2 and H2O in the feed). Advanced reaction tests highlighted outstanding materials (especially NiFe catalyst deposited onto hard-templated ceria), displaying catalytic performances able to compete with those typical of noble metal–based catalysts. Such catalysts were further investigated by means of Raman, NEXAFS, H2–TPR, and CO@FT-IR, unraveling their surface and reduction properties, which make them excellent candidates for replacing more costly noble metal-based catalysts currently employed for CO oxidation reaction.

Self-Cleaning Highly Porous TiO2 Coating Designed by Swelling-Assisted Sequential Infiltration Synthesis (SIS) of a Block Copolymer Template.

Photocatalytic self-cleaning coatings with a high surface area are important for a wide range of applications, including optical coatings, solar panels, mirrors, etc. Here, we designed a highly porous TiO2 coating with photoinduced self-cleaning characteristics and very high hydrophilicity. This was achieved using the swelling-assisted sequential infiltration synthesis (SIS) of a block copolymer (BCP) template, which was followed by polymer removal via oxidative thermal annealing. The quartz crystal microbalance (QCM) was employed to optimize the infiltration process by estimating the mass of material infiltrated into the polymer template as a function of the number of SIS cycles. This adopted swelling-assisted SIS approach resulted in a smooth uniform TiO2 film with an interconnected network of pores. The synthesized film exhibited good crystallinity in the anatase phase. The resulting nanoporous TiO2 coatings were tested for their functional characteristics. Exposure to UV irradiation for 1 h induced an improvement in the hydrophilicity of coatings with wetting angle reducing to unmeasurable values upon contact with water droplets. Furthermore, their self-cleaning characteristics were tested by measuring the photocatalytic degradation of methylene blue (MB). The synthesized porous TiO2 nanostructures displayed promising photocatalytic activity, demonstrating the degradation of approximately 92% of MB after 180 min under ultraviolet (UV) light irradiation. Thus, the level of performance was comparable to the photoactivity of commercial anatase TiO2 nanoparticles of the same quantity. Our results highlight a new robust approach for designing hydrophilic self-cleaning coatings with controlled porosity and composition.

In-situ sodium chloride template synthesis of γ-WO3 hollow cubes for high-sensing and dual-selective hydrazine/dibutylamine detection at different temperatures

The fabrication of a chemiresistive sensor with dual-selectivity to highly toxic and explosive N2H4/dibutylamine (DBA) remains challenging due to no report. To this aim, we synthesized uniform (NH4)0.33WO3 cuboid precursors through optimized solvothermal reaction and in-situ formed NaCl template. Subsequently, the precursors were calcined in air to transform into γ-WO3 hollow cubes (WO3-HC) assembled from near-spherical nanoparticles, and the effect of calcination temperature on microstructures and gas-sensing properties was investigated. Among, WO3-HC-5 obtained by calcining precursor at 500 °C has broad pore channels, large specific surface area and abundant oxygen vacancy defects. Under the catalytic synergy of surface W6+ Lewis acid with dangling bonds, WO3-HC-5 sensor realizes the bifunctional monitoring of N2H4 and DBA. It presents large response value (S = 606.6) to 100 ppm N2H4 at 50 °C and a good response (S = 76.7) to the same concentration of DBA at 217 °C, and has fast response rate, low practical detection limit, satisfactory stability and humidity resistance. WO3-HC-5 represents the first metal oxide-based sensor with dual-selectivity towards aforementioned harmful gases at different operating temperatures. Moreover, the bifunctional mechanism has been characterized and analyzed in detail.

Cryo-EM structure and functional landscape of an RNA polymerase ribozyme.

The emergence of an RNA replicase capable of self-replication is considered an important stage in the origin of life. RNA polymerase ribozymes (PR) - including a variant that uses trinucleotide triphosphates (triplets) as substrates - have been created by in vitro evolution and are the closest functional analogues of the replicase, but the structural basis for their function is poorly understood. Here we use single-particle cryogenic electron microscopy (cryo-EM) and high-throughput mutation analysis to obtain the structure of a triplet polymerase ribozyme (TPR) apoenzyme and map its functional landscape. The cryo-EM structure at 5-Å resolution reveals the TPR as an RNA heterodimer comprising a catalytic subunit and a noncatalytic, auxiliary subunit, resembling the shape of a left hand with thumb and fingers at a 70° angle. The two subunits are connected by two distinct kissing-loop (KL) interactions that are essential for polymerase function. Our combined structural and functional data suggest a model for templated RNA synthesis by the TPR holoenzyme, whereby heterodimer formation and KL interactions preorganize the TPR for optimal primer-template duplex binding, triplet substrate discrimination, and templated RNA synthesis. These results provide a better understanding of TPR structure and function and should aid the engineering of more efficient PRs.

Hexagonal CeO2 nanoplate@Au catalysts for the selective oxidation of 1,3-propanediol to a polymer platform, 3-hydroxypropionic acid at room temperature

Hexagonal CeO2 plates (H-CeO2) were prepared through template synthesis using a 2D hexagonal microporous organic polymer (H-MOP). After loading Au species onto H-CeO2, the resulting H-CeO2@Au was studied as a...

Toward three-dimensionally ordered nanoporous graphene materials: template synthesis, structure, and applications

Precise template synthesis will realize three-dimensionally ordered nanoporous graphenes (NPGs) with a spatially controlled seamless graphene structure and fewer edges.

High-fidelity synthesis of microhole templates with low-surface-energy-enabled self-releasing photolithography.

Material patterning through templates has provided an efficient way to meet the critical requirement for surface function in various fields. Here, we develop a self-releasing photolithographic process to make large-area freestanding templates with precise patterns. The low surface energy of substrates by hydrophobic treatment with proper silane modification ensures the template self-releasing. This method eliminates the need of mechanical separation or any sacrificial layers. Major steps including UV exposure and baking are optimized to realize high-quality structures and the final release of templates. The negative photoresists of SU-8 and polyimide are chosen to confirm the feasibility of this process. Wafer-scale freestanding templates with uniform microhole arrays are obtained with high structural fidelity, smooth surfaces and excellent flexibility. The hole size ranges from several to several tens of micrometers with an extremely low variation (<1%). These advantages could promote the application of precisely structured templates for surface patterning in material and surface science.

Rapid, self-sacrificing template synthesis of two dimensional high-entropy oxides toward high-performance oxygen evolution

The large size high-entropy oxides nanosheets were prepared by the self-sacrificing template method via Joule heating in a short period of time, which show high activity (1281 A g−1@1.55 V vs. RHE) and stability in alkaline OER.

Photocatalytic CO2 reduction by topologically matched polymer-polymer heterojunction nanosheets.

Conversion of solar energy into chemical fuel can be achieved through a number of routes but direct conversion, via photocatalysis, is potentially the simplest and cheapest route to the transformation of low-value substances, water and CO2, to useful chemical fuels or feedstocks such as hydrogen, formate, methanol, and syngas. 2D polymers, including carbon nitrides and COFs, have emerged as one of the most promising classes of organic photocatalysts for solar fuels production due to their energetic tunability, charge transport properties and robustness. They are, however, difficult to process and so there have been limited studies into the formation of heterojunction materials incorporating these components. In this work we use our novel templating approach to combine topologically matched imine-based donor polymers with acceptor polymers formed through Knoevenagel condensation. An efficient heterojunction interface was formed by matching the isostructural nodes and linkers that make up the D1 and A1 semiconductors and this was reflected in the increased photocatalytic activity of the heterojunction material T1. Tuning of the templating synthesis route to give heterojunctions with optimised donor : acceptor ratios, as well as the photocatalytic conditions, resulted in CO production rates that were between 1.5 and 10 times higher than those of the individual polymers. A further set of polymers A5 and D5 were developed with more optimised structures for CO2 reduction including increased overpotential for the reduction reaction and the presence of co-catalyst chelating groups. These had increased activity compared to the group 1 family and again showed higher activity for CO production by the templated heterojunction, T5, than either individual component or a physical mixture of the donor and acceptor.

Synthesis of a [2]catenane by ring closing metathesis of a [2]rotaxane prepared by crown ether active templation.

The high yielding synthesis and spectral characterization of a [2]catenane prepared by Grubbs catalyzed ring closing metathesis of a [2]rotaxane prepared by crown ether active template synthesis is described.

Employing a template synthesis to access diastereopure Np(iv) and U(iv) complexes and analysis of their 5f orbitals in bonding

A template methodology was employed as an entryway into diastereopure U(iv) and Np(iv) organometallic complexes, and the 5f orbital contributions to bonding were determined.

Synthesis and performance of binder-free porous carbon electrodes in electrochemical capacitors.

Porous binder-free carbon electrodes were obtained by impregnating cellulose filter papers with phenolic resin through soft-salt template synthesis and thermal pyrolysis. These self-standing electrodes were used directly in a supercapacitor device. To understand the impacts of filter paper (FP) thickness on carbon filter paper (CFP) morphology, porosity, and surface functionalities, five different materials were examined. The CFP electrode thickness was adjusted linearly with the FP thickness to produce electrodes ranging from 100 to ∼800 μm. As the thickness of the CFP increased, there was an increase in the specific surface area and oxygen-based functionalities. Electrochemical testing in a 1 M KOH aqueous electrolyte demonstrated that electrode thickness played a key role in electrochemical capacitor (EC) performance, i.e., capacitance enhances linearly when the electrode becomes thinner. For low thicknesses (<280 μm), the capacitance and rate capability decreased slightly with increasing thickness; for high thicknesses, the performance drastically degraded despite the high specific surface area and oxygen surface functionalities. This effect was amplified at high regimes, indicating that high electrode thicknesses and fiber diameters limited electrolyte diffusion in the applied synthesis conditions. Thus, the high material porosity was inaccessible to ion adsorption. Consequently, thinner electrodes showed the highest capacitance (197 F g-1 at 0.1 A g-1) and rate capability (81%) values, exceeding those of their traditional binder-electrode counterparts prepared under similar conditions. Finally, for alkali metal hydroxide solutions, 1 M KOH exhibited a cation match with the salt template (KCl), while CsOH achieved additional capacitance retention (88% at 10 A g-1). Complex ion adsorption mechanisms were observed through a quartz crystal microbalance.

Removal of o-Nitrophenol via Adsorption by Porous Carbon Derived from Magnesium Oxide and Waste Polyethylene Terephthalate Prepared by Template Method

In the present paper, the porous carbon material derived from waste PET was fabricated using a one-step recyclable MgO template synthesis approach. The material was subsequently employed as adsorbent for the efficient capture of o-nitrophenol (ONP) from aqueous solutions. With the change of the ratio of MgO template to waste PET, the prepared porous carbon has controllable specific surface area. The sample of WPC-1.5 exhibits a remarkable specific surface area of 885.99 m2/g. Static adsorption experiments demonstrate that this material possesses a substantial adsorption capacity for ONP, achieving a value of 474 mg/g. The WPC-1.5 was characterized by scanning electron microscopy, BET and adsorption kinetic and equilibrium isotherms evaluation.

Capture of mechanically interlocked molecules by rhodium-mediated terminal alkyne dimerisation.

The transition metal-mediated dimerisation of terminal alkynes is an attractive and atom-economic method for preparing conjugated 1,3-enynes. Using a phosphine-based macrocyclic pincer ligand, we demonstrate how this transformation can be extended to the synthesis of novel, hydrocarbon-based interlocked molecules: a rotaxane by 'active' metal template synthesis and a catenane by sequential 'active' and 'passive' metal template procedures.

Proof of principle for template synthesis approach for the radio emission from vertical extensive air showers

The radio detection technique of cosmic ray air showers has gained renewed interest in the last two decades. While the radio experiments are very cost-effective to deploy, the Monte-Carlo simulations required to analyse the data are computationally expensive. Here we present a proof of concept for a novel way to synthesise the radio emission from extensive air showers in simulations. It is a hybrid approach which uses a single microscopic Monte-Carlo simulation, called the origin shower, to generate the radio emission from a target shower with a different longitudinal evolution, primary particle type and energy. The method employs semi-analytical relations which only depend on the shower parameters to transform the radio signals in the simulated antennas. We apply this method to vertical air showers with energies ranging from 1017eV to 1019eV and compare the results with CoREAS simulations in two frequency bands, namely the broad [20, 500] MHz band and a more narrow one at [30, 80] MHz. We gauge the synthesis quality using the maximal amplitude and energy fluence contained in the signal. We observe that the quality depends primarily on the difference in Xmax between the origin and target shower. After applying a linear bias correction, we find that for a shift in Xmax of less than 150 g/cm2, template synthesis has a bias of less than 2% and a scatter up to 6%, both in amplitude, on the broad frequency range. On the restricted [30, 80] MHz range the bias is similar, but the spread on amplitude drops down to 3%. These fluctuations are on the same level as the intrinsic scatter we observe in Monte-Carlo ensembles. We therefore surmise the observed scatter in amplitude to originate from intrinsic shower fluctuations we do not explicitly account for in template synthesis.

Formation of zinc selenite nanostructures in SiO2/Si track templates with the use of two kinds of electrolytes

This paper presents studies of zinc selenite nanocrystals obtained by chemical and electrochemical deposition of zinc in a silicon dioxide track template. With the use of two kinds of electrolytes, zinc selenite nanocrystals were prepared by template synthesis and their morphological, structural and photoluminescent properties were investigated. The electrochemical deposition method was shown to be more optimal to create this crystal in comparison to the chemical deposition method. The cell parameters created by us match up with the results of other authors. Photoluminescence spectra were recorded in the spectrum interval from 2 to 4 eV at room temperature at an excitation wavelength of ~ 4 eV.