Plasmon-driven surface catalytic reaction of 4-ethynylaniline in a liquid environment

There is much evidence that surface plasmon photocatalytic reactions can occur on organic molecules on metal surfaces. In this paper, we focus on the photocatalytic reaction of 4-ethynylaniline (PEAN) on silver nanoparticles (Ag NPs) in a liquid environment by surface-enhanced Raman spectroscopy (SERS). Our experiments used SERS to characterize p,p′-diynylazobenzene produced from PEAN via a selective catalytic coupling reaction on Ag NPs. This discovery not only achieved the expected results but also broadens the known plasmon-driven surface catalytic reaction system. In our work, we also regulated the photocatalytic coupling reaction conditions of PEAN on Ag NPs by laser power-dependent and time-dependent SERS spectra.

The mechanism of Ag NP induced dimerization of PEAN was investigated by using SERS spectra. A very interesting phenomenon was discovered, that is where the relative Raman intensities of b₂ modes increased either with increasing incident laser power or exposure time.     

Development of improved dual-diazonium reagents for faster crosslinking of tobacco mosaic virus to form hydrogels

New bench-stable reagents with two diazonium sites were designed and synthesized for protein crosslinking. Because of the faster diazonium-tyrosine coupling reaction, hydrogels from the crosslinking of tobacco mosaic virus and the reagent DDA-3 could be prepared within 1 min at room temperature. Furthermore, hydrogels with the introduction of disulfide bonds viaDDA-4 could be chemically degraded by dithiothreitol. Our results provided a facile approach for the direct construction of virus-based hydrogels.

Improved dual-diazonium reagents were developed for more efficient crosslinking of tobacco mosaic virus to form hydrogels.     

Functionalization of boron-doped diamond with a push–pull chromophore via Sonogashira and CuAAC chemistry

Improving the performance of p-type photoelectrodes represents a key challenge toward significant advancement in the field of tandem dye-sensitized solar cells. Herein, we demonstrate the application of boron-doped nanocrystalline diamond (B:NCD) thin films, covalently functionalized with a dithienopyrrole–benzothiadiazole push–pull chromophore, as alternative photocathodes. First, a primary functional handle is introduced on H-terminated diamond via electrochemical diazonium grafting. Afterwards, Sonogashira cross-coupling and Cu(i) catalyzed azide–alkyne cycloaddition (CuAAC) reactions are employed to attach the chromophore, enabling the comparison of the degree of surface functionalization and the importance of the employed linker at the diamond-dye interface. X-ray photoelectron spectroscopy shows that surface functionalization via CuAAC results in a slightly higher chromophore coverage compared to the Sonogashira cross-coupling. However, photocurrents and photovoltages, obtained by photoelectrochemical and Kelvin probe measurements, are approximately three times larger on photocathodes functionalized via Sonogashira cross-coupling. Surface functionalization via Sonogashira cross-coupling is thus considered the preferential method for the development of diamond-based hybrid photovoltaics.

Functionalization of boron-doped diamond with a push–pull chromophore via Sonogashira cross-coupling affords better photovoltaic performances as compared to functionalization via CuAAC.     

Anisotropy-induced directional self-transportation of low surface tension liquids: a review

Inspired by natural surfaces such as butterfly wings, cactus leaves, or the Nepenthes alata plant, synthetic materials may be engineered to directionally transport liquids on their surface without external energy input. This advantageous feature has been adopted for various mechanical and chemical processes, e.g. fog harvesting, lubrication, lossless chemical reactions, etc. Many studies have focused on the manipulation and transport of water or aqueous droplets, but significantly fewer have extended their work to low surface tension (LST) liquids, although these fluids are involved in numerous industrial and everyday processes. LST liquids completely wet most surfaces which makes spontaneous transportation an active challenge. This review focuses on recently developed strategies for passively and directionally transporting LST liquids.

The passive transportation of liquids is comprehensively reviewed specifically for low surface tension fluids.     

7-Alkoxy-appended coumarin derivatives: synthesis,photo-physical properties,aggregation behaviours and current–voltage (I–V) characteristic studies on thin films

In this study, we designed and synthesised a series of coumarin derivatives appended with a long alkoxy chain on the seventh position of the coumarin-3-carboxylate/carboxylic acid core to make thin film materials. Synthesised compounds were characterized by their UV and fluorescence spectra in solutions as well as their films prepared by both LB and spin-coated methods. The surface morphology and electrical behaviour of thin films were judged by AFM, SEM and I–V characteristic mapping respectively. Isotherm, UV-Vis absorption and fluorescence spectroscopic investigations revealed the formation of aggregates on thin films. The result of SEM and AFM images provides the information about the length and height of aggregates on the thin films of coumarin derivatives. From I–V characteristics, it was found that at room temperature, the spin-coated films of coumarin derivatives containing an ester functional group exhibited a threshold switching behaviour, whereas derivatives containing the carboxylic acid functional group showed both threshold and bipolar switching behaviours. We also noticed that the I–V characteristic features of synthesized materials depended on the length of the alkyl chain of individual series.

In this article, we demonstrate the design, synthesis and physico-chemical characteristics, including electrical switching behaviours of long alkoxy-appended coumarin carboxylate/carboxylic acid in thin films.     

Insight into the adsorption of a liquid organic hydrogen carrier,perhydro-i-dibenzyltoluene (i = m,o, p), on Pt,Pd and PtPd planar surfaces

Liquid organic hydrogen carriers (LOHCs) are considered to be safe and efficient hydrogen storage media with high hydrogen storage capacities. Adsorption of the LOHC perhydro-i-dibenzyltoluene (i = meta (m), ortho (o), para (p)) isomers on (100), (110) and (111) planar surfaces of Pd, Pt and a 50 : 50 PtPd alloy were investigated, using density functional theory with van der Waals corrections. The calculated heats of formation of the isomers indicated that all the isomers considered were energetically stable. Surface selectivity to isomer adsorption was investigated, using isomer adsorption preference and energies. The (110) surface was found to be highly preferred by the different isomers, compared with both the (100) and the (111) surfaces. Among the isomers, isomer–surface attachment occurred most often in the case of perhydro-m-dibenzyltoluene and perhydro-o-dibenzyltoluene adsorption. The LOHC isomer adsorption on different surfaces was found to be spontaneous, energetically stable and exothermic, with high isomer adsorption preference for Pt and PtPd surfaces, compared with Pd surfaces. This indicates the ease of loading of the LOHC on Pt and PtPd surfaces, for subsequent dehydrogenation.

Liquid organic hydrogen carrier (LOHC) interaction with a planar surface of a catalyst.     

Strain-enhanced giant Rashba spin splitting in ultrathin KTaO3 films for spin-polarized photocurrents

Strong Rashba effects at semiconductor surfaces and interfaces have attracted great attention for basic scientific exploration and practical applications. Here, we show through first-principles investigation that applying biaxial stress can cause tunable and giant Rashba effects in ultrathin KTaO₃ (KTO) (001) films with the most stable surfaces. When increasing the in-plane compressive strain to −5%, the Rashba spin splitting energy reaches E_R = 140 meV, corresponding to the Rashba coupling constant α_R = 1.3 eV Å. We investigate its strain-dependent crystal structures, energy bands, and related properties, and thereby elucidate the mechanism for the giant Rashba effects. Further calculations show that the giant Rashba spin splitting can remain or be enhanced when capping layer and/or Si substrate are added, and a SrTiO₃ capping can make the Rashba spin splitting energy reach the record 190 meV. Furthermore, it is elucidated that strong circular photogalvanic effect can be achieved for spin-polarized photocurrents in the KTO thin films or related heterostructures, which is promising for future spintronic and optoelectronic applications.

Strong Rashba effects at semiconductor surfaces and interfaces have attracted attention for exploration and applications. We show with first-principles investigation that applying biaxial stress can cause tunable and giant Rashba effects in ultrathin KTaO₃ (KTO) (001) films.     

Synthesis and characterisation of fluorinated epitaxial films of BaFeO2F: tailoring magnetic anisotropy via a lowering of tetragonal distortion

In this article, we report on the synthesis and characterisation of fluorinated epitaxial films of BaFeO₂F via low-temperature fluorination of thin films of BaFeO_2.5+d grown by pulsed laser deposition. Diffraction measurements show that fluoride incorporation only results in a contraction of the film perpendicular to the film surface, where clamping by the substrate is prohibitive for strong in-plane changes. The fluorinated films were found to be homogenous regarding the fluorine content over the whole film thickness, and can be considered as single crystal equivalents to the bulk phase BaFeO₂F. Surprisingly, fluorination resulted in the change of the tetragonal distortion to a nearly cubic symmetry, which results in a lowering of anisotropic orientation of the magnetic moments of the antiferromagnetically ordered compound, confirmed by Mössbauer spectroscopy and magnetic studies.

Fluorination of epitaxially grown thin films of BaFeO_2.5 to BaFeO₂F results in increased magnetic anisotropy.     

Graphene oxide membrane chemically modified by electron-transfer diazonium chemistry for efficient dye separation

By chemical modification of the graphene oxide (GO) surface via diazonium chemistry, we introduce nitrobenzene groups as new interlayer pillars to GO memebranes like the surface oxygen-containing functional groups. The larger pillar can finely enlarge the interlayer space of the GO membrane. The filtration performance of modified GO membranes with different mass ratios of nitrobenzene diazonium tetrafluoroborate (NDT) were tested for EB, DR81, and MB. Notably, when the GO : NDT ratio is 1 : 1, it is found that the water flux can be enhanced by more than twice and by nearly 1.4 times its value for EB and DR81, respectively, while maintaining a high rejection (92% for EB and 95% for DR81). In conclusion, the chemical modification of GO through the dediazonization reaction of NDT can indeed improve the separation efficiency of the dye.

By diazonium chemistry, nitrobenzene groups have been introduced to graphene oxide membranes as interlayer pillars like the surface oxygen-containing functional groups.     

The study of cationic waterborne polyurethanes modified by two different forms of polydimethylsiloxane

Two kinds of dimethylpolysiloxane, KF-6001 and X-22-176-DX, were used to modify polyurethane. The effects of KF-6001 and X-22-176-DX on the colloidal, physico-chemical and surface properties were studied for polydimethylsiloxane modified cationic waterborne polyurethanes (SiCWPUs). The chemical structures and the surface morphologies of the SiCWPUs are characterized via Fourier transform infrared spectrometry and scanning electron microscopy. The results showed that the addition of siloxane changes the structure and surface morphology of the polyurethane. The element distributions in the polymer films were tested via X-ray photoelectron spectroscopy, and the effect of the hydrophobicity of the surfaces of the polymer films of the cationic waterborne polyurethanes was demonstrated via water contact angle tests on the surfaces of the films. As the amount of siloxane added increases, the silicon content on the surfaces of the SiCPWU1 films increases from 0% to 17.92%, and the actual silicon content on the surfaces of the films was much larger than the theoretical value. Therefore, the hydrophobicity of the membrane surface increases sharply, and the contact angle increases from 63.0° to 105.3°. Dynamic mechanical analysis indicates that the introduction of polydimethylsiloxane into the cationic aqueous polyurethane chain increases microphase separation in the polymer films. Stress–strain data showed that the mechanical properties of SiCPWU1 films were better than those of SiCPWU2 films when the same amounts of PDMS were added.

Two kinds of dimethylpolysiloxane, KF-6001 and X-22-176-DX, were used to modify polyurethane.     

Effect of lattice mismatch on film morphology of the quasi-one dimensional conductor K0.3MoO3

High quality epitaxial thin films of the quasi-one dimensional conductor K_0.3MoO₃ have been successfully grown on SrTiO₃(100), SrTiO₃(110), and SrTiO₃(510) substrates via pulsed laser deposition. Scanning electron microscopy revealed quasi-one dimensional rod-shaped structures parallel to the substrate surface, and the crystal structure was verified by using X-ray diffraction. The temperature dependence of the resistivity for the K_0.3MoO₃ thin films demonstrates a metal-to-semiconductor transition at about 180 K. Highly anisotropic resistivity was also observed for films grown on SrTiO₃(510).

High quality epitaxial thin films of the quasi-one dimensional conductor K_0.3MoO₃ have been successfully grown on SrTiO₃(100), SrTiO₃(110), and SrTiO₃(510) substrates via pulsed laser deposition.     

Strain coupling of ferroelastic domains and misfit dislocations in [101]-oriented ferroelectric PbTiO3 films

High-index perovskite ferroelectric thin films possess excellent dielectric permittivity, piezoelectric coefficient, and exotic ferroelectric switching properties. They also exhibit complications in the ferroelastic domains, misfit dislocations, and strain-relaxation behaviors. Exploring the relationship of the ferroelastic domains and misfit dislocations may be of benefit for promoting the high-quality growth of these thin films. Here, the strain field of the ferroelastic domains and misfit dislocations in [101]-oriented PbTiO₃/(La, Sr)(Al, Ta)O₃ epitaxial thin films were investigated by advanced aberration-corrected (scanning) transmission electron microscopy (TEM) combined with geometry phase analysis (GPA). Two types of misfit dislocations with projected Burgers vectors of a[001] or a[100] on the (010) plane were elucidated, whose strain fields included in-plane strain and lattice rotation coupled with the c domains above them. Besides, it was demonstrated that the coupling was kept inside the PbTiO₃ films when the film thickness was increased. Furthermore, the polarization rotation was observed in both narrow c domains and around the misfit dislocation cores, which may be attributed to the flexoelectric effect. These results are expected to provide useful information for understanding the nucleation and propagation mechanism of ferroelastic domains and for further modifying the growth of high-index ferroelectric thin films.

The strain coupling of misfit dislocations and ferroelastic domains is revealed in [101]-oriented PbTiO₃/(La, Sr)(Al, Ta)O₃ films and flexoelectric-induced polarization rotation is observed around the misfit dislocation cores.     

Rational and site-selective formation of coordination polymers consisting of d10 coinage metal ions with thiolate ligands using a metal ion-doped polymer substrate

Here, we report an interfacial approach for fabricating coordination polymers (CPs) consisting of d¹⁰ coinage metal ions with thiolate ligands on a polymer substrate. It was found that CPs were selectively formed on the polymer substrate, resulting in the formation of CP-based thin films. In addition, utilizing a mixed metal ion-doped polymer substrate leads to the formation of mixed-metal CP-based films.

We report an interfacial approach for fabricating coordination polymer (CP) crystal films and patterns on a polymer surface using a metal ion-doped polymer substrate.     

Large refractive index changes in ZIF-8 thin films of optical quality

ZIF-8 (zeolitic imidazolate framework-8) is a member of the growing family of metal–organic frameworks (MOFs). Homogeneous and crack-free ZIF-8 thin films of optical quality were crystallized on silicon and glass substrates. The refractive index of such ZIF-8 thin films in the complete visible light spectrum was directly determined for the first time. By incubating the porous films in different substances, the refractive index could be modulated over a wide range, two times larger than previously reported for MOF thin films. Reversible refractive index switching in ZIF-8 thin films was performed via the liquid and the gas phase. The ability to adjust the refractive index over a broad range enables the use of ZIF-8 films for applications in optical devices such as sensors, coatings for mirrors and lenses, or as an optical medium in more complex optical devices.

The refractive index (RI) of ZIF-8 thin films with optical quality was determined over the whole visible spectrum. The RI can be fine-tuned over a wide range by loading with different organic guest molecules for various optical applications.     

Functionalized quinolizinium-based fluorescent reagents for modification of cysteine-containing peptides and proteins

A series of quinolizinium-based fluorescent reagents were prepared by visible light-mediated gold-catalyzed cis-difunctionalization between quinolinium diazonium salts and electron-deficient alkyne-linked phenylethynyl trimethylsilanes. The electron-deficient alkynyl group of the quinolizinium-based fluorescent reagents underwent nucleophilic addition reaction with the sulfhydryl group on cysteine-containing peptides and proteins. The quinolizinium-based fluorescent reagents were found to function as highly selective reagents for the modification of cysteine-containing peptides and proteins with good to excellent conversions (up to 99%). Moreover, the modified BCArg mutants bearing cationic quinolizinium compounds 1b, 1d, 1e and 1h exhibit comparable activity in enzymatic and cytotoxicity assays to the unmodified one.

New quinolizinium-based fluorescent reagents were made by visible light-mediated gold-catalyzed cis-difunctionalization of quinolinium diazonium salts and trimethylsilyl alkyne derivatives.     

Combining a ligand photogenerator and a Ru precatalyst: a photoinduced approach to cross-linked ROMP polymer films

Although metathesis photoinduced catalysis is now well established, there is little development in thin film preparation using photochemically activated ring-opening metathesis polymerization (ROMP). Herein, a N-heterocyclic carbene (NHC) photogenerator (1,3-bis(mesityl)imidazolium tetraphenylborate) is combined with an inactive metathesis catalyst ([RuCl₂(p-cymene)]₂) to generate under UV irradiation an active catalyst (p-cymene)RuCl₂ (NHC), that is capable of producing in a single step cross-linked copolymer films by ROMP of norbornene with dicyclopentadiene. The study shows that the photoinitiated catalytic system can be optimized by increasing the yield of photogenerated NHC through a sensitizer (2-isopropylthioxanthone), and by choosing [RuI₂(p-cymene)]₂ as precatalyst to provide a long-term photolatency. The cross-linked polymer structure is investigated by a range of techniques including gel content measurement, FT-IR and solid-state ¹³C NMR spectroscopy, TGA and DSC, which reveal a cross-linking mechanism proceeding through both metathesis and olefin coupling.

Photoactivated ROMP is harnessed for the single-step formation of cross-linked polymer coatings based on norbornene and dicyclopentadiene.     

In situ synchrotron XAS study of the decomposition kinetics of ZDDP triboreactive interfaces

One of the major obstacles in replacing the widely used zinc dialkyldithiophosphate (ZDDP) antiwear additive with a more environmentally friendly one is the difficulty of time-resolving the surface species resulting from its decomposition mechanism under high contact pressure and temperature. To tackle this issue, a newly developed miniature pin-on-disc tribotester was coupled with synchrotron X-ray absorption spectroscopy (XAS) to perform in situ tribological tests while examining the composition of the formed triboreactive films. The results showed that in the case of bare steel surfaces the initial decomposition products are mainly zinc sulfate species, which with further shearing and heating are reduced to zinc sulfide mixed with metal oxides. The mixed base layer seems to enhance the tenacity of the subsequently formed zinc phosphate layers composing the main bulk of the protective triboreactive film. This base layer was not observed in the case of coated substrates with hydrogenated diamond-like carbon (a-C:H DLC) coating, which results in the formation of less durable films of small volume barely covering the contacting surfaces and readily removed by shear. Comprehensive decomposition pathways and kinetics for the ZDDP triboreactive films are proposed, which enable the control and modification of the ZDDP triboreactive films.

Surface chemistry of phosphate triboreactive layers formed on uncoated and DLC coated steel surfaces as revealed by a novel in situ synchrotron-tribotester.     

A novel Au/electroactive poly(amic acid) composite as an effective catalyst for p-nitrophenol reduction

A Au/electroactive poly(amic acid) (Au/EPAA) composite was synthesized and characterized, and its catalytic ability was evaluated. EPAA was synthesized via oxidative coupling polymerization and Au nanoparticles were anchored to the amino and carboxyl groups. The Au/EPAA composite was characterized via X-ray diffraction analysis, X-ray photoelectron spectroscopy, and scanning electron microscopy, which confirmed that the Au nanoparticles were well dispersed on the EPAA surface. p-Nitrophenol was reduced to p-aminophenol within 5 min at room temperature, with a rate constant of 0.84 min⁻¹. Cycling measurements showed that the Au/EPAA composite achieved higher than 92% conversion. The Au/EPAA composite showed excellent performance and stability as a catalyst for the reduction of p-nitrophenol to p-aminophenol.

The Au/EPAA composite demonstrated excellent performance and stability as a catalyst for the reduction of p-nitrophenol to p-aminophenol.     

The effect of solvent on Al-doped ZnO thin films deposited via aerosol assisted CVD

Aluminium-doped zinc oxide (AZO) thin films were deposited via aerosol assisted chemical vapour deposition (AACVD) from zinc acetylacetonate and aluminium chloride at 450 °C. The precursor solutions consisted of methanol in a mixture with one other secondary solvent, including toluene, tetrahydrofuran, n-hexane, cyclohexane, and ethyl acetate. The crystal structures, elemental compositions and surface morphologies of the resulting AZO films were determined, as well as the optoelectronic properties. It was found that the more polar solvents enhanced growth in the (002) plane of the wurtzite crystal structure, and that solutions with low viscosities resulted in superior grain growth. The film deposited from a solution consisting of methanol and ethyl acetate displayed the lowest visible transmittance, due to carbon contamination. However, it also exhibited 60% lower resistivity, in comparison to the film deposited using methanol only. This suggests that optoelectronic properties can be tuned for specific photovoltaic devices.

Aluminium-doped zinc oxide (AZO) thin films were deposited via aerosol assisted chemical vapour deposition (AACVD) from zinc acetylacetonate at 450 °C.     

Stable polymer brushes with effectively varied grafting density synthesized from highly crosslinked random copolymer thin films

We demonstrate the synthesis of poly(methyl methacrylate) (PMMA) and poly(styrene-b-methyl methacrylate) (P(S-b-MMA)) brushes on crosslinked random copolymer thin films, compositionally varied poly(styrene-r-glycidyl methacrylate) (P(S-r-GMA)), which can be further functionalized with a molecule featuring an initiator group upon crosslinking to form highly stable thin films. With careful optimizations, PMMA brushes were successfully grown from the surfaces of initiator functionalized P(S-r-GMA) via surface-initiated atom transfer radical polymerization. The grafting densities of the PMMA and P(S-b-MMA) brushes were effectively controlled to be in different density regimes by controlling the composition of P(S-r-GMA) and post-crosslinking functionalization methods. Synthesized BCP brushes were stable upon repetitive washing and thermal annealing processes even at high grafting density, highlighting that the outstanding stability of crosslinked P(S-r-GMA) thin films enables close examination of the morphology of thermally annealed P(S-b-MMA) brushes in different grafting density regimes.

Crosslinkable epoxy copolymers enable achieving highly stable P(S-b-MMA) brushes with controlled grafting density for close examination of phase separation behaviors.