CO ₂ electroreduction is a promising technology to produce chemicals and fuels from renewable resources. Polycrystalline and nanostructured metals have been tested extensively while less effort has been spent on understanding the performance of bimetallic alloys. In this work, we study compositionally variant, smooth Au-Pd thin film alloys to discard any morphological or mesoscopic effect on the electrocatalytic performance. We find that the onset potential of CO formation exhibits a strong dependence on the Pd content of the alloys. Strikingly, palladium, a hydrogen evolution catalyst with reasonable exchange current density, suppresses hydrogen evolution when alloyed with gold in the presence of CO ₂ . Cyclic voltammetry, in situ surface enhanced infrared absorption spectroscopy, and potential-dependent online product analysis strongly suggest that by alloying Au with Pd a significant increase in the surface coverage of adsorbed CO occurs with increasing Pd content at low overpotentials (e.g., approximately -0.35 V vs RHE). Such an increase in CO coverage suppresses H ₂ evolution due to the lack of vacant active sites. Moreover, the overall increase in the binding energy with the CO ₂ intermediates gained with the addition of Pd increases the CO production at low overpotentials, where polycrystalline Au suffers from poor CO ₂ adsorption and poor selectivity for CO production. These results show that promising CO ₂ reduction electrode materials (e.g., Au) can be alloyed not only to tune the catalyst's activity but also to deliberately decrease the availability of surface sites for competitive H ₂ evolution.

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Here, we report the covalent coupling of poly (styrene-co-maleic anhydride) onto γ-alumina to develop high-performance organic solvent nanofiltration (OSN) membranes. A high molecular weight (M _w ) alternating copolymer of maleic anhydride (MA) and styrene (St) was synthesized and directly grafted to the γ-alumina membrane, while commercially available low M _w random copolymers of St and MA were also investigated. We show that solute rejection and membrane permeability strongly depend on the nature of the applied copolymer. In particular, the M _w of the copolymer applied is potentially the key for improving the membrane performance. When a high M _w copolymer was applied, the grafted layer covered the surface of the membrane. This results in membranes with significantly improved rejection, while maintaining a high permeability. In contrast, we observed pore grafting by applying low M _w copolymers, which resulted in membranes with slightly higher rejection and dramatically lower permeability compared to unmodified membrane. The best results were obtained by grafting γ-alumina with a high M _w alternating copolymer. These membranes showed a solute rejection of 98% for Sudan Black B (457 g mol ⁻¹ ) in toluene, while the permeability remained high at 2.9 L m ⁻² h ⁻¹ bar ⁻¹ .

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We report an advanced treatment method for phosphoric acid recovery from leached sewage sludge ash. Layer-by-layer (LbL) polyelectrolyte deposition has been used as a tool to modify and convert a hollow ultrafiltration membrane into a nanofiltration (NF) LbL membrane for H₃PO₄ recovery. To build the LbL membrane, poly(styrenesulfonate) PSS was chosen as polyanion, while three different polycations were used: a permanently charged polyelectrolyte, poly(diallyldimethylammonium chloride), PDADMAC; a pH-dependent charged polyelectrolyte poly(allylamine hydrochloride), PAH; and a PAH modified with guanidinium groups (PAH-Gu). Based on detailed surface characterizations (AFM, XPS and Zeta-potential) it was concluded that both charge density and pH-responsiveness of the polycations are key parameters to control the final membrane surface structure and transport properties. The surface properties of LbL-coated membranes were correlated with the membrane filtration performance, when exposed to the real leached sewage sludge ash solution. The highest permeability was recorded for (PDADMAC/PSS)₆, a result that was rationalized on its loose, and possibly less interpenetrated, structure, followed by (PAH-Gu/PSS)₆ characterized by a more dense, compact layer. H₃PO₄ recovery was the highest in the case of (PDADMAC/PSS)₆, but the retention of multivalent metals (Fe³⁺ and Mg²⁺) was low, leading to a more contaminated permeate. The opposite trend was observed for (PAH-Gu/PSS)_6, resulting in a less metal-contaminated, but also a less H₃PO₄-concentrated permeate. Our LbL-modified membranes were found to improve the permeability and H₃PO₄ recovery compared to a commercially available acid-resistant NF membrane.

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We calibrate the lateral mode AFM (LFM) by determining the position-sensitive photodetector (PSPD) signal dependency on the lateral tip displacement, which is analogous to the constant-compliance region in normal-force calibration. By stick-slip on stiff, amorphous surfaces (silica or glass), the lateral tip displacement is determined accurately using the feedback loop control of AFM system. The sufficiently high contact stiffness between the Si AFM tip and stiff, amorphous surfaces substantially reduces the error of PSPD signal dependency on the lateral tip displacement. No damage or modification of the AFM probe is involved and only a clean silicon or glass wafer is needed.

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Preparation methods are presented of thin dual layer membranes (DLM's) and mixed matrix membranes (MMM's) based on nanosheets of the Cu-BDC metal-organic framework (MOF, lateral size range 1–5 µm, thickness 15 nm) and commercially available poly(ethylene oxide)–poly(butylene terephthalate) (PEO–PBT) copolymer (Polyactive™) and their performances are compared in CO₂/N₂ separation. The MMMs and DLMs represent two extremes, on the one hand with well-mixed components and on the other hand completely segregated layers. Compared to the free-standing membranes, the thin PAN- and zirconia-alumina-supported MMMs showed significant enhancement in both permeance and selectivity. The support properties affect the obtained selective layer thickness and its resistance impacts the CO₂/N₂ selectivity. The permeance of thin DLM's is among the highest reported literature data of MOF based thin MMMs, but have a modest selectivity. Addition of the nanosheets in the thin MMMs improves the CO₂/N₂ selectivity of the already selective polymer further to 77. The nanosheets in the thin MMMs make a gutter layer on the PAN support superfluous. The small pore support ZrO₂-alumina does not need a gutter layer. XRD analysis reveals that the spatial distribution of MOF nanosheets and polymer chains packing were responsible for differences in the permeation performance of the free-standing, thin dual layer and mixed matrix membranes.

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The preparation and the performance of mixed matrix membranes based on metal-organic polyhedra (MOPs) are reported. MOP fillers can be dispersed as discrete molecular units (average 9 nm in diameter) when low filler cargos are used. In spite of the low doping amount (1.6 wt %), a large performance enhancement in permeability, aging resistance, and selectivity can be achieved. We rationalize this effect on the basis of the large surface to volume ratio of the filler, which leads to excellent dispersion at low concentrations and thus alters polymer packing. Although membranes based only on the polymer component age quickly with time, the performance of the resulting MOP-containing membranes meets the commercial target for postcombustion CO₂ capture for more than 100 days.

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Recently various porous organic frameworks (POFs, crystalline or amorphous materials) have been discovered, and used for a wide range of applications, including molecular separations and catalysis. Silicon nanowires (SiNWs) have been extensively studied for diverse applications, including as transistors, solar cells, lithium ion batteries and sensors. Here we demonstrate the functionalization of SiNW surfaces with POFs and explore its effect on the electrical sensing properties of SiNW-based devices. The surface modification by POFs was easily achieved by polycondensation on amine-modified SiNWs. Platinum nanoparticles were formed in these POFs by impregnation with chloroplatinic acid followed by chemical reduction. The final hybrid system showed highly enhanced sensitivity for methanol vapour detection. We envisage that the integration of SiNWs with POF selector layers, loaded with different metal nanoparticles will open up new avenues, not only in chemical and biosensing, but also in separations and catalysis.

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This paper describes a novel method to fabricate porous graphene oxide (PGO) from GO by exposure to oxygen plasma. Compared to other methods to fabricate PGO described so far, e.g. the thermal and steam etching methods, oxygen plasma etching method is much faster. We studied the development of the porosity with exposure time using atomic force microscopy (AFM). It was found that the development of PGO upon oxygen-plasma exposure can be controlled by tapping mode AFM scanning using a Si tip. AFM tapping stalls the growth of pores upon further plasma exposure at a level that coincides with the fraction of sp² carbons in the GO starting material. We suggest that AFM tapping procedure changes the bond structure of the intermediate PGO structure, and these stabilized PGO structures cannot be further etched by oxygen plasma. This constitutes the first report of tapping AFM as a tool for local mechano-chemistry.

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We have investigated in detail properties of hybrid polyelectrolyte-anion exchange membranes (AEMs) having different amounts of a guanidinium-modified poly(allylamine hydrochloride) (PAH-Gu) derivative (2, 5, and 8 wt%). The presence of guanidinium groups at the membrane surface was confirmed by XPS. For 2 and 5 wt% the blended membranes are homogeneous, while at 8 wt% segregation is observed by AFM. The membrane permselectivity and ionic electrical resistance for phosphate reduce upon incorporation of the PAH-Gu in the membrane, reflecting an increased co-ion (H⁺ and Na⁺) permeation. We conclude that PAH-Gu loaded in the AEM favors an interaction with phosphate. In electrodialysis, using sodium sulfate and sodium dihydrogen phosphate at equal concentrations in the source phase a slight preference for phosphate was observed. Our work shows that this facile membrane fabrication procedure shows great potential in terms of tuning the membrane properties. One way to boost selective ion transport could be by increasing the number of functional groups in the membrane.

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Atomic Force Microscopy (AFM) can not only image the topography of surfaces at atomic resolution, but can also measure accurately the different interaction forces, like repulsive, adhesive and lateral existing between an AFM tip and the sample surface. Based on AFM, various extended techniques have been developed such as colloidal probe AFM, single molecule AFM, bio-AFM, Kalvin probe AFM and lateral force AFM (LFM). Together,these make AFM a powerful tool to study the properties of surfaces and interfaces, which is of great importance for many different disciplines, e.g. surface chemistry, polymerchemistry and physics, solid-state physics, cell biology and medicine.@en

The Hamaker constant between graphene oxide and silica, which quantifies the strength of van der Waals forces is determined, by mimicking a “vacuum spacer” in an atomic force microscopyforce study. It is demonstrated that, a 2D spacer is expected to yield an accurately defined separation, owing to the high atom density and strength in planar direction compared with other dimensional spacers. @en

We have prepared (AB)n-multiblock copolymers based on N-(3′-hydroxyphenyl)trimellitimide (IM), 4- hydroxybenzoic acid (HBA), and 6-hydroxy-2-naphthoic acid (HNA) via a simple one-pot melt condensation method. The blocky nature is the result of phase separation taking place in the early stages of the melt polymerization process. The liquid crystal HBA/HNA fraction phase separates from the isotropic HBA/IM fraction and this phase separation effectively shuts down transesterification reactions, preventing randomization of the polymer backbone. The (AB)n-multiblock copoly- (esterimide)s exhibit two distinct glass transition temperatures (Tgs). The first Tg at ∼120 °C can be assigned to the HBA/HNA rich A-block and the second Tg at ∼220 °C can be assigned to the HBA/IM rich B-block. When introducing imide-based phenylethynyl end-groups, these reactive functionalities end-up exclusively at the termini of the HBA/IM rich B-blocks, effectively forming a phenylethynyl-terminated B(AB)n-reactive oligomer. Upon thermal treatment, cross-linking via the phenylethynyl end-groups results in a thermoset where the Tg of the B-block increases by as much as ∼106 °C. The Tg of the HBA/HNA A-block remains unchanged. Scanning electron microscopy experiments show a gradual change in morphology, from a typical fibrous LCP texture for the HBA/HNA rich polymers to a more consolidated morphology for the HBA/IM rich polymers. Atomic force microscopy images confirm the presence of two distinct domains when 44 mol % of HBA was replaced by IM. The “hard” imide rich B-blocks form domains of ∼100−200 nm that are embedded in the imide poor or “soft” A-blocks. @en