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Porous carbons based on activated reduced graphene oxide (rGO) have been demonstrated as excellent sorbents for U(vi), with their sorption capacity correlating with the degree of their oxidation. Herein, we demonstrate an extraordinarily high U(vi) sorption of ∼7050 μmol g−1 for super-oxidized porous carbon (SOPC) with a specific surface area (SSA) of ∼970 m2 g−1 and an extremely high degree of oxidation (C/O = 2.1), similar to graphene oxide. The SOPC materials were prepared using an oxidation treatment applied to activated carbon produced from spruce cones. The extremely high SSA of the precursor activated carbon (∼3400 m2 g−1) as well as its microporous structure and mild oxidation treatment allowed for the preservation of a significant part of the surface area, providing materials with rather narrow pore size distribution (∼7.5 Å). The SOPC prepared from spruce cone biochar is similar to defective graphene oxide but with a significantly higher surface area, resulting in superior U(vi) sorption. Analysis of EXAFS and XPS data shows that U(vi) likely binds to carboxylic groups on the opposite sides of the micropores. The small size of the micropores and irregular pore wall structure are the main factors affecting pore sorption. The spruce-cone biochar has a strong advantage compared with earlier used rGO as a precursor for the preparation of SOPC.

Using molten salts for etching aluminum (Al) away from the MAX phase for MXene synthesis is an attractive alternative method that allows one to avoid the use of toxic hydrofluoric acid (HF) solutions. However, the mechanism of the MAX phase reaction with molten salts remains to date unclear due to the lack of in situ data. Here, we present a detailed in situ time-resolved synchrotron radiation X-ray diffraction study of the MAX phase annealing in molten ZnCl₂ and SnCl₂. The reaction of salts with the MAX phase is found to occur in two stages. The initial period of annealing results in the delamination of two-dimensional (2D) Ti₃C₂ layers, vigorous evolution of AlCl₃ bubbles, and dissolution of Zn in a ZnCl₂ melt. The chlorine-terminated Ti₃C₂ sheets formed in the delaminated state are restacked into a relatively well-ordered MXene structure (P6₃/mmc, a = 3.071 Å and c = 18.577 Å) during the prolonged annealing in molten salts. Surprisingly, the data recorded directly in molten salts at temperatures up to 873 K demonstrate that Ti₃C₂Cl_x MXene shows no swelling in both liquid ZnCl₂ and SnCl₂. The structure of MXene studied directly in the molten salts is found to be the same as in ex situ experiments performed after cooling and water washing under ambient conditions. The absence of the “pristine” melt-swollen phase indicates a rather different mechanism of MXene formation compared to HF-based solution methods. Formation of MXene by gradually removing Al from the MAX phase starting at the edges of flakes and propagating into the deeper parts of interlayers is not possible, since the molten salt is not capable of penetrating between Cl-terminated Ti₃C₂ layers.

Ti-MXene is a promising electrode material for supercapacitors. The layered structure of MXene expands due to swelling in electrolytes allowing the penetration of ions into the interlayers. A study of effects related to the match between the size of cations in hydrated or dehydrated state and the interlayer distance of MXene is performed here using operando X-ray diffraction (XRD) in capillary-size supercapacitors with alkali metal chloride electrolytes. The supercapacitors are studied during charging and discharging over several cycles revealing structural changes at both MXene electrodes. Experiments reveal an expansion of the MXene c-lattice in LiCl, NaCl, and KCl electrolytes (compared to the expansion in pure water) under an increase of applied voltage from 0 to 1 V and structural oscillations related to a change of polarity. The interlayer spacing of MXene remains close to the water-swollen state in RbCl, CsCl, and NH4Cl electrolytes showing no further expansion as a function of applied voltage. Only rather small variations of interlayer spacing are found in H2SO4 electrolyte during tens of charge–discharge cycles. Analysis of the match between the sizes of ions and the width of MXene interlayers demonstrates that some cations and anions could be inserted into MXene interlayers only in dehydrated state.

Graphite oxides (GO) swell in liquid alcohols with significant expansion of c-lattice. However, temperature-dependent swelling of Hummers GO (HGO) has so far been reported only for methanol and ethanol. Here, HGO swelling in liquid 1-alchohols (C1 to C22 according to the number of carbons) is studied as a function of temperature using in situ synchrotron radiation XRD. Swelling transitions never previously observed for HGO in any kind of polar solvents are found, enthalpy of these transition and compositions of HGO-Cx solid solvates near the point of solvent melting reported. Swelling transitions from low temperature to high-temperature phase are found for HGO in C10–C22 alcohols, similarly to earlier reported transitions in Brodie graphite oxide (BGO). The transitions correspond to a strong change of inter-layer distance correlating with the alcohol molecules length and change in molecules orientation from perpendicular to parallel to GO planes (Type II transitions). However, Type I swelling transitions (related to insertion/removal of one layer of alcohol molecules) reported earlier for BGO are not found in HGO. Continuous changes of the d(001) spacing are revealed for HGO immersed in all smaller alcohols in the range C1 (methanol) to C9 (nonanol).

Very strong difference in many properties is well documented for graphite oxides (GtO) synthesized by Brodie (BGO) and Hummers (HGO) methods. The difference is typically assigned to the type of oxidant (chlorates or KMnO4, respectively). However, not only oxidants but also acids used in these methods are different. It is still unclear which of the different properties of GtO are dependent on the oxidant or acid used in the synthesis. Here we synthesized a new type of graphite oxide using an oxidation agent typical for the Brodie method (KClO3) in combination with acids so far used only in modified Hummers' method (H2SO4+H3PO4). The GtO synthesized by this method (MGO) demonstrates some properties similar to BGO (higher temperature of exfoliation and less defected structure) but also similarity to some other properties of HGO (absence of sharp swelling transitions). Comparing MGO, BGO, and HGO allows us to distinguish the effects of acids and oxidants on the properties of graphite oxides. The new procedure proposed in this study allows preparation of GtO nearly free from hole/vacancy defects (similarly to BGO) but avoids dangerous HNO3. MGO is suggested as a favorable precursor for the preparation of graphene films by thermal or chemical reduction methods.

Super-oxidized porous carbons produced from reduced graphene oxide have been demonstrated recently to show unique sorption properties. Here we report experiments with identical oxidative treatment applied to four very different types of porous carbon materials with extremely broad range of specific surface area (SSA) ∼350–3400 m²g⁻¹. It is demonstrated that KOH-activated carbons can be oxidized to the same degree as graphene oxide (GO) while preserving a larger part of SSA. Prolonged oxidation with ammonium persulfate resulted in extraordinary high degree of oxidation with C/O ratio reaching 2.1. Precursor carbons with largest share of micropores are found to be more stable against oxidative treatment, while single-walled carbon nanotubes (SWCNT's) are oxidized to much less extent. While mesopores collapse, micropores survive strong oxidation treatment providing materials with rather narrow pore size distribution and high (for given oxidation degree) BET SSA up to ∼1150 m²g⁻¹. Super-oxidized porous carbons (SOPC's) show a high abundance of hydroxyl, epoxide, carbonyl, and carboxyl functional groups (similar to GO). As a result of oxidation, the hydrophobic carbons are converted into hydrophilic materials. Characterization shows that many properties of SOPC (e.g. degree of oxidation, type of functional groups, thermal stability etc.) are rather similar to GO, except for three-dimensional porous structure which can be considered an advantage for sorbent applications. SOPC's demonstrate superior sorption capacity for Cu(II) (up to ∼105 mgg⁻¹), which is 8-fold higher than the value for non-oxidized precursor.

Electrochemical synthesis of graphene oxide (GO) is known to occur with potential oscillations, but the structural changes underlying these oscillations have remained unclear. In situ time-resolved synchrotron radiation X-ray diffraction demonstrates that the electrochemical synthesis of GO in aqueous H₂SO₄ can be described as an oscillating reaction. The transformation from graphite to GO proceeds through periodic structural oscillations that correlate with potential cycles. Stage-1 graphite intercalation compound (GIC) is found only at the peak of the potential cycle, but not at the bottom of the cycle. Stage-1 GIC is formed in the first half-cycle from stage-2 GIC and then transforms into "pristine graphite oxide" (PGO) on the lower side of the potential cycle, after which the cycle restarts with the formation of a new portion of stage-1 GIC. Water-washing results in the transformation of PGO into water-swollen GO with d(001) ~11 Å. These periodic structural changes can be considered a new type of oscillating reaction. The presented results provide broad insights into the oscillating structural changes occurring during the anodic graphite oxidation in aqueous H₂SO₄ and allow to update of the mechanism of GO electrochemical formation.

Many applications are suggested for Ti-MXene motivating strong interest in studies of Ti₃C₂T_x synthesis by solution-based methods. However, so far only ex situ studies of the synthesis are performed, mostly due to the difficulty of handling HF-based solutions. Here the first time-resolved in situ synchrotron radiation X-ray Diffraction study of MXene synthesis performed using a plastic capillary-size reaction cell directly in HF solution is reported. This study provides the first report on the structure of “pristine MXene” formed by Ti₃AlC₂ etching with LiF+HCl. The term “pristine” refers to the MXene structure found directly in HF solution. By comparing the interlayer distances of pristine MXene (≈13.5 Å), solvent-free Li-intercalated MXene (≈12.2 Å), and Li-free MXene (≈10.7 Å), it can be concluded that the width of “slit pores” formed by terminated MX layers during the Al etching does not exceed ≈3 Å. The width of these slit pores is a key factor for HF etching of Al within the interlayers. This space constraint explains the slow kinetics of MXene formation in HF-based synthesis methods. No intermediate phases are observed, suggesting that the crystalline MXene phase is formed by the simultaneous etching of Al and termination of Ti₃C₂ layers.