Biorefinery strategies that convert renewable lignocellulosic biomass into high-value xylooligosaccharides (XOS) are of great significance for reducing dependence on fossil resources and advancing sustainable biomass utilization. In recent years, the efficient production of XOS has attracted increasing attention because of its broad applications in food, feed, and health-related sectors. With the rapid development of XOS production technologies, a timely and critical overview of recent progress is needed. This review comprehensively summarizes the current progress in XOS production from lignocellulosic biomass, focusing on feedstock selection, production strategies, purification technologies, applications of XOS, and machine learning-assisted process optimization. The one-step organic acid hydrolysis is a promising XOS production strategy because of its operational simplicity, effective conversion yield, relatively mild reaction conditions, lower corrosion risk, and potential to enable the coproduction of multiple value-added products in biomass biorefineries. Deep eutectic solvent (DES) pretreatment strategies are also promising approaches for XOS production. In addition, the major challenges associated with industrial-scale XOS production are discussed, particularly in relation to the development of low-cost enzyme systems, efficient byproduct utilization, machine learning-assisted prediction and optimization of production parameters, and process integration. Overall, this review provides an updated perspective for the sustainable, efficient, and industrially relevant production of XOS.
The electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) offers a sustainable route for biomass valorization, yet its efficiency is limited by insufficient catalyst activity and selectivity. Herein, we report a highly active Co single-atom catalyst anchored on fractionated lignin-derived carbon for HMF electrooxidation. By employing a solvent-based fractionation process, a low-molecular-weight lignin fraction (EHL-1 K, similar to 1 kDa) with uniform structural and chemical properties is obtained, which serves as an ideal precursor for constructing atomically dispersed Co-N-4 sites. The resulting Co@EHL-1 K catalyst achieves outstanding HMF conversion (100%), FDCA selectivity (98.87%), and Faradaic efficiency (98.06%) at a low applied potential of 1.46 V vs. RHE in 1.0 M KOH. X-ray absorption spectroscopy confirms the exclusive presence of Co-N coordination without detectable Co-Co bonds, verifying the atomically dispersed nature of Co species. Density functional theory calculations reveal that the Co-1-N@EHL model exhibits a significantly stronger formation energy (-8.31 eV) and HMF adsorption energy (-0.783 eV) compared to the Co-4@EHL model (-3.09 eV and -0.497 eV, respectively), elucidating the thermodynamic stability and enhanced reactivity of Co-N-4 sites. Combined spectroscopic and electrochemical analyses further demonstrate that the Co-N-4 centers, embedded in a conductive N-doped carbon framework, facilitate efficient multi-electron transfer.
This study investigated the electrocatalytic oxidative process of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) using Co/N-doped carbon catalysts derived from lignin subjected to different pretreatment methods, including enzymatic hydrolysis lignin (EHL), alkali lignin (AL), and kraft lignin (KL). The EHL-derived catalyst exhibited superior activity, achieving a current density of 110 mA cm(-2) at 1.5 V vs. RHE along with 98% HMF conversion, 99.02% FDCA selectivity, and 98.4% Faradaic efficiency (FE). Structural characterizations and theoretical calculations revealed that the preserved aromatic framework of EHL promoted the formation of atomically dispersed Co-N-x active sites and facilitated efficient HMF adsorption. The computational results further demonstrated that the optimized electronic structure of the Co-N-x sites reduced the activation energy for the rate-determining step. This work demonstrated a direct correlation between the pretreatment history of lignin and its electrocatalytic performance, offering a precursor-based design strategy for efficient HMF electrooxidation.
Herein, a novel hydrothermal synthesis strategy is proposed for the preparation of novel Cu-Ce MOF heterojunction nano catalysts (CuCeOX/C) for 5-hydroxymethylfurfural (HMF) electrooxidation reaction in this paper. CuCeOX/C exhibits superior catalytic performance, with the current density of CuCeOX/C reaching 100 mA cm- 2 at a low potential of 1.408 V vs. RHE, and doubling to 280 mA cm- 2 at a lower potential of 1.5 V vs. RHE. Under these conditions, the conversion of HMF reaches 100 %, with a selectivity of over 99.11 % for 2,5-furan dicarboxylic acid (FDCA) and a Faradaic efficiency of 97.76 %. Theoretical calculations and In-situ-EIS have demonstrated that Ce-based Cu-MOF heterojunction nanocatalysts enhance the adsorption energy of the CuCeOX/C catalysts on HMF substrates while also decreasing reaction energy barrier of HMFOR. Based on our work, the employment of CeCu/MOF heterojunction electrocatalysts for efficient electro-oxidation of HMF to FDCA paves a green and sustainable way for advancing sustainable chemical processes and biomass valorization.
A straightforward and scalable in situ pyrolysis method was developed to synthesize palladium-boron nitride (Pd/BN) nanocatalysts using melamine, boric acid, and palladium acetate as precursors. The strong electronic interaction between Pd nanoparticles and the BN support facilitates charge transfer at the interface, thereby enhancing catalytic activity. The as-prepared Pd/ BN catalyst exhibited excellent performance in Suzuki reactions under ambient conditions, achieving up to 99 % yield across a broad range of aryl bromides and boronic acids. The reaction was conducted in a green EtOH/H2O (1:1) solvent system and required only a low Pd loading (0.25 mol%). In addition to its high efficiency, the catalyst demonstrated remarkable recyclability and retained activity over at least ten consecutive cycles with minimal deactivation. Density functional theory (DFT) calculations, supported by experimental data, revealed that the Pd/BN interface lowers the energy barrier of the rate-determining transmetalation step, thus accelerating the overall reaction. This study not only provides a sustainable catalytic system for efficient C-C bond formation under mild and environmentally benign conditions but also offers valuable insights into the rational design of electron-rich heterogeneous catalysts through metal-support interaction engineering.
The lack of high-performance, low-cost electrocatalysts is the key challenge for the production of 2,5 furandicarboxylic acid via electrocatalytic oxidation of 5-hydroxymethylfurfural. In this work, we report a novel approach for the preparation of highly dispersible transition metal catalysts loaded by carbon aerogel-loaded via a chitosan-transition-metal-ion coordination. The experimental results demonstrated that all of Ni2+, Co2+ and Cu2+ were able to coordinate with chitosan to form stable gels, which were then pyrolyzed to obtain highly dispersed transition metal-based catalysts (Co@NC, Ni@NC and Cu@NC) The Cu@NC exhibited the best HMFOR activity with high HMF conversion (nearly 100 %), FDCA selectivity (98.1 %), and Faraday efficiency (95.3 %). Mechanistic studies showed that Cu@NC was able to accumulate more effective oxidatively active species and thus achieve higher HMFOR current density compared to Co@NC and Ni@NC, and that the electrooxidation of HMF at the Cu@NC electrode followed the HMFCA oxidation pathway. This study provides a general and facile strategy for macropreparation of highly dispersible carbon aerogel-loaded transition metal catalysts for efficient electrocatalytic valorization of HMF.
In this study, a novel Co-modified MoS2 loaded spherical biochar (Co-MoS2@BC) derived from renewable biomass was synthesized as an efficient anodic HMFOR electrocatalyst. In the HMFOR process, the Co-MoS2@BC required a potential of only 1.426 V for the current density of 100 mA/cm2, significantly outperforming that of the MoS2 loaded on spherical biochar (MoS2@BC) and the Co nanoparticles loaded on spherical biochar (Co@BC). Furthermore, the HMF conversion ratio reached 99.6 %, FDCA selectivity was 99.7 %, and Faradaic efficiency was 99.3 %. The Mechanistic studies reveal that the modified-Co on the MoS2 modulated the electronic structure of Co-MoS2@BC, which not only enhanced the interaction between Co-MoS2@BC and the electrolyte, thereby facilitating the evolution of the catalysts toward highly active species, but also improved the adsorption of HMF and the H+ transfer e- coupling step during the HMFOR process.
Efficient utilization of renewable biomass resources is one of the feasible approaches to address the massive consumption of fossil fuels accompanying severe resource crises and environmental pollution. Currently, 2,5-furandicarboxylic acid derived from the oxidation of biomass-based 5-hydroxymethylfurfural (HMF) is a valuable chemical as the alternative to the fossil resource-derived terephthalic acid. However, the development of high-performance and low-cost Cu-based electrocatalysts for the efficient HMF oxidation reaction (HMFOR) remains an enormous challenge. Guided by our theoretical prediction, we proposed a coordination-pyrolysis strategy to fabricate highly dispersed copper sulfide (CuS) nanosheets supported on N-doped porous carbon precatalyst (CuS@NC). The covalent S species trigger the deep reconstruction of CuS nanosheets, and the in situ generated SO42− not only promotes the formation of Cu2+δ species but also facilitates the cleavage of α–C–H and –O–H bonds in HMF. The optimized CuS@NC achieved a high current density of 335 mA cm−2 at 1.50 V vs. reversible hydrogen electrode, representing a remarkable 628% enhancement over the control catalyst. This study integrates theoretical predictions with experimental investigations to systematically elucidate how S species promote the deep reconstruction of CuS nanosheets to enhance the HMFOR performance and proposes a scalable strategy for preparing ultra-uniform transition metal sulfide precatalysts.
Herein, a novel ball milling-pyrolysis strategy was proposed for preparing a highly dispersed Ni3Fe nanoalloy catalyst (Ni3Fe@NC) used for 5-hydroxymethylfurfural (HMF) electro-oxidation reaction. The Ni3Fe@NC delivered a high current density of 100 mA cm- 2 at a low potential of 1.467 V vs RHE, with a HMF conversion rate of over 99.6 %, 2,5-furan dicarboxylic acid (FDCA) selectivity of 97.1 % and a Faraday efficiency of 96.7 %. Theoretical calculations, in-situ EIS, quasi-in-situ XRD and XPS demonstrated that Fe-doping optimizes the electronic structure of Ni3Fe@NC and regulates its d-band center, which not only promoted the reconstruction of Ni3Fe@NC to form high-oxidation-activity Ni2+delta and Ni3+delta species but also reduced the reaction barrier of the key rate-determining step (*5-Hydroxymethyl-2-furancarboxylic acid (HMFCA)->*5-formyl-2-furancarboxylic acid (FFCA)) during HMFOR. Based on this interesting work, we provided a facile macroscopic preparation strategy on highly dispersed nanoalloy catalyst for efficient electro-oxidation of HMF.
Exploring lignin depolymerization and modification can yield high-value chemicals and liquid fuels, thereby enhancing resource utilization efficiency and alleviating pressure caused by energy shortages. In this paper, lignin-based carbon materials (Co-ZIF@KL-1 and Co-ZIF@KL-2) loaded with a metal-organic framework (ZIF-67) on kraft lignin biochar (KL) were prepared using two different methods (In situ method and traditional immersion method). In addition, catalysts with Co metal loaded on KL biochar (Co@KL) and ZIF-67 catalyst were also prepared for comparison with the above two different Co-ZIF@KL-1 and Co-ZIF@KL-2 catalysts. These catalysts were all applied to the hydrodeoxygenation (HDO) of guaiacol. Among them, the Co-ZIF@KL-1 catalyst exhibited the highest catalytic activity with 94.53% conversion of guaiacol and 83.86% selectivity of cyclohexanol under the optimal reaction conditions of 240 degrees C, 2.0 MPa N2, and 4 h. The superior catalytic performance can be attributed to its high surface area, strong stability, and appropriate acidic sites. Based on the distribution of catalytic products, pathways for the guaiacol HDO reaction are hypothesized. In general, ZIF materials and lignin composites offer substantial value for advancing biomass catalytic conversion in the future. Exploring lignin depolymerization and modification can yield high-value chemicals and liquid fuels, thereby enhancing resource utilization efficiency and alleviating pressure caused by energy shortages.
Implantation of intraocular lens after combined procedure of vitrectomy and cataract surgery is usually required to reduce the postoperative refraction errors. However, because of the severe fibrosis of the anterior capsule and the adhesion between the anterior and posterior capsules, it is difficult to reopen the capsular bag to complete the secondary IOL implantation. We describe here a surgical approach for reopening the severe adhesion between capsules and removing the significant fibro-proliferative membranous material by injecting viscoelastic agent into the periphery of the capsular bag to separate the anterior and posterior capsules. The IOL was implanted into the capsular bag without any zonular rupture or posterior capsule tear. The position of the intraocular lens was stable during postoperative follow-ups up to 3 months. Our procedure to open a severely fibrosis capsule is safe and effective, and may be used as a preferred method.
Pt-based nanomaterials have attracted considerable attention as electrocatalysts for direct alcohol fuel cells. Nevertheless, their widespread application as electrocatalysts has been seriously impeded by the high price and slow reaction kinetics of Pt. In order to decrease the Pt content and enhance the electrocatalytic properties, a simple and effective solvothermal method was proposed for the preparation of ternary star-like PdPtNi nanostructures (NSs) with a spiny surface. The ethanol oxidation reaction under alkaline conditions was used as a model to evaluate the electrocatalytic properties of the samples. The experimental results indicated that the PdPtNi NSs displayed better electrochemical activity and durability than those of commercial Pt black catalysts. Their perfect electrocatalytic performances could be attributed to the large specific surface area, abundant reactive sites, and synergy effects of the different metals. The preparation of spiny star-like PdPtNi NSs will be an avenue for the synthesis of high-performance electrocatalysts for direct ethanol fuel cells.
We have constructed biocompatible antibacterial nanoplatforms on the basis of a hybrid hydrogel via simple electrostatic interaction embedded with thin layer graphene oxide (GO) sheets modified with zinc oxide quantum dots (ZnO QDs). The materials possess favorable antibacterial efficacy, thereby providing excellent killing effect for Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) compared with materials that have single diagnosis and treatment mode. The excellent performance stems from the combined effects of hyperthermia produced under the near-infrared irradiation of GO sheets, reactive oxygen species, the release of Zn2+ from ZnO QDs under acidic environment, and the antibacterial activity of hydrogel. The synergy of antibacterial nanoplatforms can be used for wound anti-inflammatory in vivo indicated by the wound healing results. The hybrid hydrogel causes no evident side effects to major organs in mice during wound healing. Therefore, the biocompatible multimodal therapeutic nanoplatforms have great potential for antibacterial activity and wound healing.
Novel multifunctional core-shell nanoparticles (NPs) have attracted widespread attention due to their easy-to-modify surface properties and abundant functional groups. This study introduces a facile approach to synthesize Ag@ iron oxide (Fe3O4) @C NPs, and modify with amino-poly (ethylene glycol) (PEG)-carboxyl and folate (FA) on the exposed carbon surface to produce high contrast for excellent stability, good biocompatibility, cancer cell targeting, and synergistic treatment. The multi-armed PEG at the edge of Ag@Fe3O4@C NPs provides the materials an excellent capacity for doxorubicin (DOX) loading. The carbon layer could be used as a photothermal reagent due to its excellent near-infrared (NIR) absorbance capacity, and Fe3O4 was used as a reagent for magnetic resonance (MR) imaging. In vivo combination therapy with this agent was administered in a mouse tumor model, and a remarkable synergistic antitumor effect that is superior to that obtained by monotherapy was achieved. Concerning these features together, these unique multifunctional Ag@Fe3O4@C-PEG-FA/DOX NPs could be regarded as an attractive nanoplatforms for chemo-photothermal synergistic tumor therapy with dual-modal fluorescence and MR imaging-guided targeting.
Exploiting high-performance and inexpensive electrocatalysts for methanol electro-oxidation is conductive to promoting the commercial application of direct methanol fuel cells. Here, we present the facile synthesis of echinus-like PdCu nanocrystals (NCs) via a one-step and template-free method. The echinus-like PdCu NCs possess numerous straight and long branches which can provide abundant catalytic active sites. Owing to the novel nanoarchitectures and electronic effect of PdCu alloy, the echinus-like PdCu NCs manifest eminent electrocatalytic performances toward methanol oxidation reaction in alkaline mediums. The mass activity of echinus-like PdCu NCs is 1202.1 mA mg Pd -1 , which is 3.7 times of Pd/C catalysts. In addition, the echinus-like structure as a kind of three-dimensional self-supported nanoarchitectures endows PdCu NCs with significantly enhanced stability and durability. Hence, the echinus-like PdCu NCs have a prospect of being employed as electrocatalysts for direct alcohol fuel cells.
This work launches the first-ever report on the fabrication of waterborne epoxy-graphene oxide (GO) coatings (WEGC) using a block polymer as a dispersant of GO, wherein the block polymer was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylic acid and oligo(ethylene glycol) methyl ether methacrylate A number of analytical techniques, such as Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD), thermo gravimetric analysis (TGA), and salt spray tests, were utilized to explore the morphology and performance of the WEGC. It was confirmed that POEGMA950-b-PAA attached to the GO nanosheets, increasing the integral space of the sheets. Modified GO (MGO) layers were well-dispersed in the epoxy matrix through the formation of a GO-dispersant-epoxy ternary molecular structure. Furthermore, the presence of MGO substantially influenced the thermal properties, mechanical properties, and anticorrosion performance of the WEGC. TGA, salt spray tests, and pull-off testsshowed that 0.5 wt.% MGO content achieved the greatest improvement in the evaluated properties.
Multicomponent Pt-based nanowires (NWs) have attracted widespread attention as eletrocatalysts toward direct alcohol fuel cells because of their unique one-dimensional structure and high reaction dynamics. Quaternary PtPdAuTe NWs are designed via a facile template method, and NWs with a different composition are obtained by adjusting the feed ratio of metal precursors. The direct displacement reaction of metal precursors with Te NWs and the partial oxidation of Te lead to the formation of quaternary NWs. The rough surface and abundant reactive sites deriving from the rearrangement of metal atoms on the Te NWs surface endow the PtPdAuTe NWs with a superior electrocatalytic property and durability for methanol oxidation. The Pt20 Pd20 Au10 Te50 NWs display the largest mass activity and best stability among all catalysts. The preparation of PtPdAuTe NWs could provide a viable strategy for the preparation of other multicomponent NWs.
Black phosphorus quantum dots (BPQDs) are gaining popularity for applications in various fields because of their unique advantages. For biomedical applications, good biosafety is a prerequisite for the use of BPQDs in vivo. However, currently, little information is available about their basic properties and biocompatibility, which are of great importance for potential biomedical applications. In this work, we prepared BPQDs by an improved solvothermal method and evaluated their fluorescence, biocompatibility, and photothermal therapy (PTT) effectiveness. First, the structures and functions of the BPQDs were investigated at the cellular and molecular levels. It was found that the fluorescence of the BPQDs is wavelength-dependent and that they absorb in the UV-vis range; also, their quantum yield reached 10.2%. In particular, we considered the morphology and lysis of human red blood cells, in vivo blood coagulation, and plasma recalcification profiles. We found that the BPQDs have excellent biocompatibility and hemocompatibility with blood components. Overall, concentrations of the BPQDs ≤0.5 mg mL-1 had few adverse effects on blood components. The resulting BPQDs can efficiently convert near-infrared (NIR) light into heat; thus, they are suitable as a novel nanotheranostic agent for PTT of cancer. Meanwhile, the results of serum biochemistry tests revealed that the indicators were at similar levels for mice exposed to BPQDs and for control mice. Furthermore, from biodistribution analysis of the BPQDs, no apparent pathological damage was observed in any organs, especially in the spleen and kidneys, during the 30 day period. Our research indicates that the BPQDs have bio-imaging capability and biocompatibility and highlights their great potential in the therapy of cancer.
Exploitation of highly active catalysts for alcohol electrooxidation is urgent for direct alcohol fuel cells (DAFCs). In this research, a facile and mild synthetic approach is utilized to control and tailor the morphology of the three-dimensional (3D) urchin-like Pd@PtNi nanostructures (NSs), and the formation mechanism of the as-prepared nanostructures is expounded in detail. The Pd@PtNi NSs exhibit outstanding electrochemical properties and remarkable durability toward both methanol and ethanol oxidation reaction (MOR and EOR) in alkaline solution. The electrochemically active surface area (ECSA) of the Pd@PtNi NSs is 59.5 m(2) g(-1), and their mass activities for MOR and EOR are 1614.3 and 1502.3 mA mg(-1) respectively, which are much higher than those of their ternary or binary alloy counterparts as well as commercial Pt black catalysts. Moreover, it still retains high current densities after catalyzing 10 000 s, while the current densities of other nanocatalysts reduce to nearly zero. The outstanding electrochemical activities and durability are owing to the specific 3D urchin-like nanostructures providing enormous active sites for catalytic reaction and the synergy effects between Pt, Pd, and Ni atoms. The 3D urchin-like Pd@PtNi NSs will enrich the electrocatalysts for DAFCs.
Zwitterion-modification, as a bioinspired strategy, provides greatly promising platforms for biological detection and sensor applications. A green, low-cost and straight-forward method for synthesis of highly fluorescent biomimetic carbon quantum dots (BCQDs) has been developed via pyrolysis of cytidine diphosphate choline (CDPC) and ethylenediamine. The BCQDs with a strong emission at wavelength of 450 nm shows ultrasensitive sensing capability for vitamin B12 with high selectivity. Using the fluorometric assay, the detection limit (DL) for vitamin B12 was found to be as low as 81 nM. Meanwhile, the results of 3-(4,5)-dimethylthiahiazo(-z-y1)-3,5-di-phenytetrazoliumromide (MTT), hemolysis measuring and morphological characterization of Red blood cells (RBCs) confirms the excellent biocompatibility of BCQDs. The imaging experiments of human cervical cancer cells (HeLa) certify that BCQDs could be served as an effective fluorescent sensing probe for label-free sensitive and selective detection of vitamin B12 in biological samples on account of their low toxicity and good biocompatibility. The BCQDs, further, were successfully applied to probe vitamin B12 in living cells, which broaden its potential application in vivo system.