The green synthesis of a palm empty fruit bunch-derived sulfonated carbon acid catalyst and its performance for cassava peel starch hydrolysis

A sulfonated carbon acid catalyst (C–SO₃H) was successfully generated from palm empty fruit bunch (PEFB) carbon via hydrothermal sulfonation via the addition of hydroxyethylsulfonic acid and citric acid. The C–SO₃H catalyst was identified as containing 1.75 mmol g⁻¹ of acid and 40.2% sulphur. The surface morphology of C–SO₃H shows pores on its surface and the crystalline index (CrI) of PEFB was decreased to 63.8% due to the change structure as it became carbon. The surface area of the carbon was increased significantly from 11.5 to 239.65 m² g⁻¹ after sulfonation via hydrothermal treatment. The identification of –SO₃H, COOH and –OH functional groups was achieved using Fourier-transform infrared spectroscopy. The optimal catalytic activity of C–SO₃H was achieved via hydrolysis reaction with a yield of 60.4% of total reducing sugar (TRS) using concentrations of 5% (w/v) of both C–SO₃H and cassava peel starch at 100 °C for 1 h. The stability of C–SO₃H shows good performance over five repeated uses, making it a good potential candidate as a green and sulfonated solid acid catalyst for use in a wide range of applications.

A sulfonated carbon acid catalyst (C–SO₃H) was successfully generated from palm empty fruit bunch (PEFB) carbon via hydrothermal sulfonation via the addition of hydroxyethylsulfonic acid and citric acid.     

Opal promotes hydrothermal carbonization of hydroxypropyl methyl cellulose and formation of carbon nanospheres

Hydrothermal carbon nanospheres were prepared by introducing opal into the hydrothermal carbonization system of hydroxypropyl methyl cellulose (HPMC). Then the effects of opal on hydrothermal carbonization of HPMC were investigated after different reaction durations (105–240 min). The reaction products were characterized by elemental analysis, gas chromatography-mass spectrometry (GC-MS), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR) and N₂ adsorption–desorption. Results of elemental analysis indicated that the H (hydrogen) and O (oxygen) content of HPMC decreased through dehydration, demethylation, decarbonylation and hydrolysis reactions, forming hydrochar with higher carbon content. The addition of opal was confirmed to accelerate the hydrolysis of HPMC. N₂ adsorption–desorption tests and SEM analysis showed that opal with a large specific surface area adsorbed HPMC hydrolysis products, such as furans, and facilitated furan cyclodehydration on its surfaces to form cross-linked carbons, which contributed to the quick formation of hydrochar. Moreover, the adsorption by opal also inhibited hydrochar aggregation, so the final hydrothermal carbon spheres had sizes of 20–100 nm.

Carbon nanospheres were formed under the effect of opal during hydrothermal carbonization of HPMC at 230 °C.     

Fused sphere carbon monoliths with honeycomb-like porosity from cellulose nanofibers for oil and water separation

Carbon monoliths with a unique hierarchical surface structure from carbonized cellulose nanofibers were synthesized in pursuit of developing carbon materials from sustainable natural resources. Through a 2-step hydrothermal – carbonization method, TEMPO-oxidized cellulose nanofibers were turned into carbon-rich hydrochar embedded with polystyrene latex as template for 80 nm-sized pores in a honeycomb pattern, while the triblock copolymer Pluronic F-127 was used for a dual purpose not reported before: (1) an interface between the cellulose nanofibers and polystyrene particles, as well as (2) act as a secondary template as ∼1 μm micelles that form hollow carbon spheres. The use of nanofibers allowed more contact between the carbon spheres to coalesce into a working monolith while optimizing the pore structure. Oil–water separation studies have shown that carbon monoliths have high adsorption capacity due to surface area and hydrophobicity. Testing against commercially available activated carbon pellets show greater performance due to highly-developed macropores.

Carbon monoliths with a unique hierarchical surface structure from carbonized cellulose nanofibers were synthesized in pursuit of developing carbon materials from sustainable natural resources.     

Effect of salts formed by neutralization for the enzymatic hydrolysis of cellulose and acetone–butanol–ethanol fermentation

Neutralization is essential to maintain the pH for enzymatic hydrolysis of cellulose followed by fermentation of biofuels. This study investigated the effect of salts formed during the neutralization on the enzymatic hydrolysis of cellulosic materials and acetone–butanol–ethanol (ABE) fermentation. The results showed that the formed Ca-citrate salt considerably decreased the glucose release by 26.9% and 26.1% from Avicel and sulfuric acid-pretreated hybrid Pennisetum, respectively, which was probably due to the unproductive adsorption of cellulases by Ca-citrate solids. On the other hand, the formed soluble Na and Ca salts severely inhibited ABE fermentation, thereby decreasing the ABE concentration from 12.8 g L⁻¹ to 0–10.7 g L⁻¹ in different degrees, but no or slight inhibition was observed when the Ca salts formed as precipitates. In particular, Ca-sulfate did not show apparent inhibition of both hydrolysis and fermentation. Therefore, the selection of suitable pretreatment and neutralizing reagents is an alternative way to avoid process inhibition in biofuel production from lignocellulosic materials.

The salts formed by neutralization after sulfuric, acetic, and citric acid pretreatments affected enzymatic hydrolysis of lignocellulosic materials and acetone–butanol–ethanol (ABE) fermentation to various degrees.     

Improved hydrogen evolution performance by engineering bimetallic AuPd loaded on amino and nitrogen functionalized mesoporous hollow carbon spheres

A highly efficient heterogeneous catalyst was synthesized by delicate engineering of NH₂-functionalized and N-doped hollow mesoporous carbon spheres (NH₂–N-HMCS), which was used for supporting AuPd alloy nanoparticles with ultrafine size and good dispersion (denoted as AuPd/NH₂–N-HMCS). Without using any additives, the prepared AuPd/NH₂–N-HMCS catalytic formic acid dehydrogenation possesses superior catalytic activity with an initial turnover frequency value of 7747 mol H₂ per mol catalyst per h at 298 K. The excellent performance of AuPd/NH₂–N-HMCS derives from the unique hollow mesoporous structure, the small particle sizes and high dispersion of AuPd nanoparticles and the modified Pd electronic structure in the AuPd/NH₂–N-HMCS composite, as well as the synergistic effect of the modified support.

Anchoring ultrafine AuPd on NH₂-functionalized and N-doped hollow mesoporous carbon spheres for formic acid dehydrogenation.     

Microwave aided conversion of cellulose to glucose using polyoxometalate as catalyst

The viability of biorefining technology primarily depends on the facile cellulose conversion route with adequate conversion efficiency. Here we have demonstrated the microwave-assisted hydrolysis of cellulose to glucose using polyoxometalate (POM) clusters as acid catalysts. Two different types of POM, including Wells–Dawson and Keggin were justified as catalysts in the cellulose conversion process. In particular, the cellulose to glucose catalytic conversion using Wells–Dawson type POMs has not been reported to date. Also, even though there have been some previous reports about the catalytic biomass conversion of Keggin type POMs, the systematic study to optimize the conversion efficiency in terms of catalyst amount, reaction temperature, reaction time, and the amount of solvent is lacking. Under the experimental conditions employed, the Keggin-type catalyst showed higher cellulose conversion and glucose yield than the Wells–Dawson-type catalyst. Furthermore, the cellulose conversion efficiency and glucose yields were optimized by tuning the reaction conditions including temperature, reaction time, and the amount of solvent. Under optimized conditions, the Keggin-type POM catalyst shows a remarkably high glucose yield of 77.2% and a cellulose conversion of 90.1%. The unique complex properties of the POM catalyst, including being (i) strong acids with extremely high Brønsted and Lewis acidity and (ii) efficient microwave adsorbants which enhanced interaction between substrate and the catalyst can be attributed to the outstanding efficacy of the conversion process.

The polyoxometalate (POM) catalysed conversion of cellulose to glucose is demonstrated. A remarkably high cellulose conversion of 90.1% with a glucose yield of 77.2% were achieved.     

Mechanochemistry-assisted hydrolysis of softwood over stable sulfonated carbon catalysts in a semi-batch process

The hydrolysis of lignocellulose is the first step in saccharide based bio-refining. The recovery of homogeneous acid catalysts imposes great challenges to the feasibility of conventional hydrolysis processes. Herein, we report a strategy to overcome these limitations by using stable sulfonated carbons as solid acid catalysts in a two-step process, composed of mechanocatalytic pretreatment and secondary hydrolysis in a semi-batch reactor. Without mechanocatalytic pre-treatment the hydrolysis of the insoluble substrate largely occurs through homogeneously catalyzed reactions. Ball-milling induced amorphization promotes a substantially higher substrate reactivity, because homogeneous hydrolysis occurs preferentially from less ordered structural domains in cellulose. In contrast, concerted ball-milling (CBM) of cellulose with the sulfonated carbon promotes a heterogeneously catalyzed hydrolysis to soluble oligosaccharides. By performing an in-depth physicochemical characterization of cellulose subjected to CBM treatment with different carbons, we reveal the crucial role of strong Brønsted acid sites in facilitating mechanocatalytic depolymerization. Recyclability experiments confirmed that despite being subject to profound structural changes during repeated pre-treatment/semi-batch hydrolysis cycles, the sulfonated carbon retained its catalytic activity. The combination of mechanocatalytic pretreatment with strong solid acids and hydrolysis in the semi-batch reactor was successfully extrapolated for the first time to the hydrolysis of real lignocellulose to achieve quantitative yields in C₅ and high yields in C₆ derived products.

A two-step process employing stable sulfonated carbons, overcomes the challenging recyclability of mineral acids used in conventional hydrolysis processes.     

Boron/nitrogen co-doped carbon synthesized from waterborne polyurethane and graphene oxide composite for supercapacitors

We report B/N co-doped carbon materials synthesized by an efficient and easy one-step carbonization method with ferric catalyst treatment from a precursor with boric acid treatment after the formation of the composite between waterborne polyurethane (WPU) and graphene oxide (GO). The nitrogen content was improved with the introduction of numerous melamine in the synthetic process of WPU. In addition, WPU possessed a repetitive basic unit urethane bond (–NHCOO); thus, nitrogen heteroatom could be efficiently introduced into the WPU/GO composite from WPU as a nitrogen-rich carbon. In addition, the specific surface area was increased by the boric acid treatment and washing process. The ferric catalyst treatment could prevent the formation of inert B–N bonds. Thus, the synthesized B/N co-doped carbon materials exhibited high specific capacitance (330 F g⁻¹ at 0.5 A g⁻¹), superior rate performance, and excellent cycling stability. Furthermore, the assembled symmetric supercapacitor displayed a good energy density (7.9 W h kg⁻¹ at 505 W kg⁻¹) and a good capacitance retention of about 89.9% after 5000 charge–discharge cycles in 6 M KOH electrolyte. Therefore, the as-prepared B/N co-doped carbon materials show a promising future in supercapacitor application.

We report B/N co-doped carbon materials synthesized by a carbonization method with ferric catalyst treatment from a precursor with boric acid treatment after the formation of the composite between waterborne polyurethane and graphene oxide.     

Principle understanding towards synthesizing Fe/N decorated carbon catalysts with pyridinic-N enriched and agglomeration-free features for lithium–oxygen batteries

Metal-N-decorated carbon catalysts are cheap and effective alternatives for replacing the high-priced Pt-based ones in activating the reduction of oxygen for metal–air or fuel cells. The preparation of such heterogeneous catalysts often requires complex synthesis processes, including harsh acid treatment, secondary pyrolysis processes, etching, etc., to make the heteroatoms evenly dispersed in the carbon substrates to obtain enhanced activities. Through combined experimental characterizations, we found that by precise control of the precursors added, a Fe/N uniformly distributed, agglomeration-free Fe/N decorated Super-P carbon material (FNDSP) can be easily obtained by a one-pot synthesis process with distinctly higher pyridinic-N content and elevated catalytic activity. An insight into this phenomenon was carefully demonstrated and also verified in Li–O₂ batteries, which delivered a high discharging platform of 2.85 V and can be fully discharged with a capacity of 5811.5 mA h g_{carbon+catalyst}⁻¹ at the cut-off voltage of 2.5 V by the low-cost Super-P modified catalyst.

Synthesizing a pyridinic-N enriched and agglomeration-free Fe/N-decorated carbon catalyst for lithium–oxygen batteries.     

Berberine-based carbon dots for selective and safe cancer theranostics

Fluorescent berberine-based carbon dots (Ber–CDs) were prepared through a facile synthesis strategy. Ber–CDs exhibited excellent optical properties for bioimaging and retained the biofunctions of berberine, and enabled selective and safe anti-tumor performance, demonstrating their promising application potential in cancer theranostics.

Fluorescent berberine-based carbon dots (Ber–CDs) were prepared through a facile synthesis strategy.     

Nanoscale tungsten nitride/nitrogen-doped carbon as an efficient non-noble metal catalyst for hydrogen and oxygen recombination at room temperature in nickel–iron batteries

A nanoscale tungsten nitride/nitrogen-doped carbon (WN/NC) catalyst was synthesized through a facile route, and it exhibited efficient catalytic performance for hydrogen and oxygen recombination at room temperature with an average catalytic velocity of 140 μmol h⁻¹ g_cat⁻¹ and long catalytic life of 954 660 s without decay in the catalytic performance. With the WN/NC catalyst, a nickel–iron battery could be sealed and maintenance-free, and it also exhibited low cost; thus, the nickel–iron battery can be used for large-scale energy storage systems in rural/remote areas.

A nickel–iron battery with nanoscale WN/NC catalyst can be used for large-scale energy storage systems in rural/remote areas.     

High ion adsorption densities of site-selective nitrogen doped carbon sheets prepared from natural lignin

Carbon fibers and sheets were prepared from jet-milled natural chitin and cellulose samples, and from natural lignin sample using ice-templating technique, respectively. Nitrogen doping treatments using melamine were also performed for the carbon fibers and sheets. Electric double layer capacitor (EDLC) electrode properties of the prepared carbon fibers and sheets including the nitrogen doped samples were investigated with aqueous (sulfuric acid) and organic (tetraethylammonium tetrafluoroborate in propylene carbonate) electrolytes. It was found that the nitrogen doped lignin carbon sheets having very small specific surface area of 66 m² g⁻¹ show very high EDLC capacitances of 227 F g⁻¹ and 80 F g⁻¹ determined by charge–discharge measurements at current density of 50 mA g⁻¹ for aqueous and organic electrolytes, respectively. X-ray photoelectron spectroscopy (XPS) measurements revealed that nitrogen atoms of the nitrogen doped lignin carbon sheets exist dominantly in pyridinic sites unlike other chitin and cellulose carbon fibers. We discussed that this site-selective nitrogen doping gives exceptionally high ion adsorption density per unit surface area of the nitrogen doped lignin carbon sheets.

Carbon fibers and sheets were prepared from jet-milled natural chitin and cellulose samples, and from natural lignin sample using ice-templating technique, respectively.     

Surface modification of carbon nanotubes by using iron-mediated activators generated by electron transfer for atom transfer radical polymerization

Herein, a surface-initiated activator generated by electron transfer for an atom transfer radical polymerization (AGET ATRP) system was developed on the surface of multiwall carbon nanotubes (MWCNTs) by using FeCl₃·6H₂O as the catalyst, tris-(3,6-dioxoheptyl) amine (TDA-1) as the ligand and ascorbic acid (AsAc) as the reducing agent. A wide range of polymers, such as polystyrene (PS), poly(methyl methacrylate) (PMMA) and poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA), were successfully grafted onto the surfaces. The core–shell structure of MWCNTs@PS was observed by TEM. Both Raman spectra and the results of hydrolysis of MWCNTs@PS (after extraction by THF) confirmed that the PS chains were covalently tethered onto the surfaces of the MWCNTs. Due to superior biocompatibility of the iron catalyst, the strategy of modification of MWCNTs via iron-mediated AGET ATRP provided a promising method for the controllable and biocompatible modification of nanomaterials.

A surface-initiated AGET ATRP system was developed on the surface of multiwall carbon nanotubes by using FeCl₃·6H₂O as the catalyst, tris-(3,6-dioxoheptyl) amine as the ligand and ascorbic acid as the reducing agent.     

Biosynthesis of Ag–Pd bimetallic alloy nanoparticles through hydrolysis of cellulose triggered by silver sulfate

We report a simple but efficient biological route based on the hydrolysis of cellulose to synthesize Ag–Pd alloy nanoparticles (NPs) under hydrothermal conditions. X-ray powder diffraction, ultraviolet-visible spectroscopy and scanning transmission electron microscopy-energy dispersive X-ray analyses were used to study and demonstrate the alloy nature. The microscopy results showed that well-defined Ag–Pd alloy NPs of about 59.7 nm in size can be biosynthesized at 200 °C for 10 h. Fourier transform infrared spectroscopy indicated that, triggered by silver sulfate, cellulose was hydrolyzed into saccharides or aldehydes, which served as both reductants and stabilizers, and accounted for the formation of the well-defined Ag–Pd NPs. Moreover, the as-synthesized Ag–Pd nanoalloy showed high activity in the catalytic reduction of 4-nitrophenol by NaBH₄.

We report a simple but efficient biological route based on the hydrolysis of cellulose to synthesize Ag–Pd alloy nanoparticles (NPs) under hydrothermal conditions.     

Fe,N-doped carbon spheres prepared by electrospinning method as high efficiency oxygen reduction catalyst

Electrocatalysts for the oxygen reduction reaction (ORR) are crucial in metal–air batteries, fuel cells and other electrochemical devices. In this study, iron and nitrogen co-doped carbon sphere electrocatalysts were synthesized by electrospinning and thermal treatment. According to the results, the catalyst marked as Fe–N/MCS-181 (Fe, N-doped mesoporous carbon spheres, iron nitrate nonahydrate as the iron source) has not only the highest iron content, which reaches up to 0.13%, but also a spherical shape. And its pore sizes are 11 and 35 nm. For the electrochemical performance, the onset potential (E_onset) of Fe–N/MCS-181 is −0.018 V, while the half-wave potential (E_1/2) of Fe–N/MCS-181 is −0.145 V, which is better than the commercial Pt/C catalyst (E_1/2 is −0.18 V). The durability of the Fe–N/MCS-181 catalyst is better than commercial Pt/C. After 10 000 s, the retention ratio of current density is 86.4%, while that of the commercial Pt/C catalyst is 84.2%. At the same time, the methanol tolerance of the Fe–N/MCS-181 catalyst is also excellent. After adding methanol, the current density of the Fe–N/MCS-181 catalyst has no obvious change. This study provides an easy method to fabricate a highly efficient and durable Fe, N-doped carbon catalyst for the oxygen reduction reaction.

Fe, N-doped carbon spheres as high-efficiency ORR catalysts were prepared by a facile electrospinning process.     

Zeolitic imidazole framework derived N-doped porous carbon/metal cobalt nanoparticles hybrid for oxygen electrocatalysis and rechargeable Zn–air batteries

Bifunctional electrocatalysts with high catalytic property for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are vital for high-performance zinc–air batteries (ZnABs). In this study, an efficient bifunctional electrocatalyst with hollow structure (C–N/Co (1/2)) has been successfully prepared through carbonization of ZIF-8@ZIF-67 and evaporation of Zn ions at high temperature. With Co nanoparticles encapsulated by an N-doped porous carbon matrix, the catalyst exhibits excellent stability in aqueous alkaline solution over an extended period and good tolerance to the methanol crossover effect. The integration of an N-doped graphitic carbon outer shell and Co nanoparticles enables high ORR and OER activity, as evidenced by ZnAB using the catalyst C–N/Co (1/2) in an air cathode.

An efficient bifunctional electrocatalyst with hollow structure (C–N/Co (1/2)) has been obtained through carbonization of ZIF-8@ZIF-67, which showed high ORR and OER activity, as evidenced by ZnAB using catalyst of C–N/Co (1/2) in air cathode.     

A fluorescent sensor constructed from nitrogen-doped carbon nanodots (N-CDs) for pH detection in synovial fluid and urea determination

Blue luminescent nitrogen-doped carbon nanodots (N-CDs) with pH-dependent properties were prepared from citric acid (CA), glutathione (GSH), and polyethylene polyamine (PEPA) using a two-step pyrolytic route. The N-CDs showed stable and strong emission bands at approximately 455 nm under 350 nm excitation. Moreover, the fluorescence of N-CDs can be gradually decreased by gradually increasing the pH value. A good linear relationship between the fluorescence intensity of N-CDs and the pH range of 3.0–9.0 was obtained. Thus, the response mechanism of N-CDs to pH was systematically investigated. N-CDs possessed –NH₂, –COOH, and –CONH– as active functional groups, which allowed the variable protonation/deprotonation of N-CDs to regulate the fluorescence emission intensities under changed pH values. Furthermore, upon combining urease-catalyzed hydrolysis of urea with increased pH values, a simple but effective fluorescence assay for urea was developed. The analytical performance for urea detection was the linear range of 0 to 10 mM with a detection limit of 0.072 mM. Additionally, the fluorescent sensor based on N-CDs was successfully applied for pH detection in synovial fluid and urea determination in serum.

Blue luminescent nitrogen-doped carbon nanodots (N-CDs) with pH-dependent properties were prepared from citric acid (CA), glutathione (GSH), and polyethylene polyamine (PEPA) using a two-step pyrolytic route.     

Advantage of semi-ionic bonding in fluorine-doped carbon materials for the oxygen evolution reaction in alkaline media

Metal-free carbonaceous catalysts have potential applications for oxygen evolution reaction (OER) devices because of their low-cost and abundant supply. We report that fluorine-doped carbon black is an active catalyst for OER. Fluorine-doped carbon black (F-KB) is simply synthesized by the pyrolysis of KETJENBLACK (KB) as carbon substrate with Nafion as fluorine precursor. As a result, the OER activity of F-KB is significantly higher than that of pristine KB in alkaline media. The OER catalytic activity of F-KB is found to be dependent on the quantity and characteristics of carbon-fluorine bonding (C–F) which can be controlled by the pyrolysis temperature. It is further found that the OER activity depends on the quantity of semi-ionic C–F bonds, but not covalent C–F bonds. This result proves the importance of carbon atoms with semi-ionic C–F bonds as the active sites for OER.

Fluorine-doped carbon has a higher electrocatalytic oxygen evolution activity than pristine carbon black in alkaline media. The activity of oxygen evolution and characteristics of carbon to fluorine bond are controlled by pyrolysis temperature of Nafion.     

Platinum–(phosphinito–phosphinous acid) complexes as bi-talented catalysts for oxidative fragmentation of piperidinols: an entry to primary amines

Platinum–(phosphinito–phosphinous acid) complex catalyzes the oxidative fragmentation of hindered piperidinols according to a hydrogen transfer induced methodology. This catalyst acts successively as both a hydrogen carrier and soft Lewis acid in a one pot – two steps process. This method can be applied to the synthesis of a wide variety of primary amines in a pure form by a simple acid–base extraction without further purification.

Platinum–(phosphinito–phosphinous acid) complex catalyzes the oxidative fragmentation of hindered piperidinols according to a hydrogen transfer induced methodology.     

Preparation of sulfonated ordered mesoporous carbon catalyst and its catalytic performance for esterification of free fatty acids in waste cooking oils

Sulfonated ordered mesoporous carbon (SO₃H-OMC) solid acid catalysts from sucrose were prepared using hard-template method, and their catalytic performance as well as the deactivation mechanism for esterification of free fatty acids (FFAs) in waste cooking oils (WCOs) were evaluated. Effects of sulfonation time, sulfonation temperature and hard template structure type for the textural properties and acid properties of SO₃H-OMC were systematically investigated by N₂ adsorption–desorption, FT-IR, NH₃-TPD, TEM and strong acid density analysis. The results indicated that, SO₃H-OMC(s)-6-160 catalyst, which was prepared by using SBA-15 as hard template at sulfonation time of 6 h and sulfonation temperature of 160 °C, had well-ordered mesoporous structure and high –SO₃H groups density (2.32 mmol g⁻¹). Compared with SO₃H-APC-6-160 catalyst, cation-exchange resin D072 and SO₃H-OMC(k)-6-160 catalyst, it was found that the SO₃H-OMC(s)-6-160 catalyst exhibited highest activity (FFAs conversion was 93.8%) and good stability for the FFAs esterification, attributed to its 2D-hexagonal channels and hydrophobic surface. The –SO₃H groups being leached out of SO₃H-OMC catalysts into the liquid phase (especially methanol) would be the main reason causing catalyst deactivation.

Sulfonated ordered mesoporous carbon solid acid catalysts had excellent catalytic performance for esterification of methanol with FFAs in WCOs.