Catalytic hydrogenolysis of larix bark proanthocyanidins in ionic liquids produces UV blockers with potential for use in cosmetics

The bark of larix, a major tree species in the coniferous forests of China''s Greater Khingan Mountains, is typically treated as waste. The bark is, however, rich in flavonoids, known as proanthocyanidins, although their high degree of polymerization and high molecular weight reduce their biological activity and potential applications. Ionic liquids, a new type of “green solvent”, characterized by low vapor pressure and good stability, have been developed and used as new solvents for naturally occurring macromolecules. Here, we used 1-butyl-3-methylimidazole chloride ([BMIM]Cl) as the ionic solvent to reduce the degree of polymerization of larix bark proanthocyanidins by Pd/C-catalyzed hydrogenolysis. The optimal reaction conditions, determined using an orthogonal experimental design, were: reaction temperature, 90 °C; reaction time, 1.5 h; catalyst loading, 4 g L⁻¹ (Pd/C: [BMIM]Cl); and hydrogen pressure, 2.5 MPa. Characterization of the reaction products by UV-Vis and IR spectroscopy and gel permeation chromatographys showed that they retained the proanthocyanidin structure. We showed that whilst both the native and depolymerized proanthocyanidins were able to block UV light when added to commercially available skin creams and sunscreens, the depolymerized proanthocyanidins were more effective at a given concentration. This study expands the applications of a new “green” ionic liquid solvent, provides a technical foundation for the low-cost depolymerization of larix bark proanthocyanidins, and also explores a potential high-value use for waste larix bark as the source of a UV-blocking additive for cosmetics.

Oligomeric proanthocyanidins with excellent UV resistance were prepared by hydrogenolysis in ionic liquids.     

Efficient synthesis of highly dispersed ultrafine Pd nanoparticles on a porous organic polymer for hydrogenation of CO2 to formate

Precise design of catalytic supports is an encouraging technique for simultaneously improving the activity and stability of the catalyst. However, development of efficient heterogeneous catalysts for transforming CO₂ into formic acid (FA) is still a big challenge. Herein, we report that Pd nanoparticles (NPs) based on a porous organic polymeric support containing amide and pyridine functional groups (AP-POP) can be an efficient catalyst for selective hydrogenation of CO₂ to form formate with high efficiency even under mild reaction conditions (6.0 MPa, 80 °C). Electron density of the active Pd species modulated via the interaction between pyridine nitrogen and Pd play important roles in dramatic enhancement of catalytic activity and was indicated by X-ray photoelectron spectroscopy (XPS) along with CO chemisorption. This work provides an interesting and effective strategy for precise support design to improve the catalytic performance of nanoparticles.

Precise design of catalytic supports is an encouraging technique for simultaneously improving the activity and stability of the catalyst.     

A highly efficient rod-like-CeO2-supported palladium catalyst for the oxidative carbonylation of glycerol to glycerol carbonate

A rod-like-CeO₂-supported Pd catalyst (Pd/CeO₂-r) was prepared using two-step hydrothermal impregnation and used in the oxidative carbonylation of glycerol to produce glycerol carbonate. The characterization results showed that the Pd was highly dispersed on the surface of the CeO₂-r, and metallic Pd was the main species in the catalyst. The Pd/CeO₂-r exhibited good catalytic performance for the oxidative carbonylation of glycerol. Under optimized reaction conditions, the glycerol conversion and glycerol carbonate selectivity were 93% and 98%, respectively, and turnover frequency was 1240 h⁻¹. However, because of the leaching of Pd and the growth of Pd particles, the catalyst was gradually deactivated throughout reuse.

Pd/CeO₂-r was prepared by a two-step hydrothermal-impregnation method for oxidative carbonylation of glycerol. It exhibited high activity, and glycerol conversion was 93% and glycerol carbonate selectivity was 98% with a TOF of 1240 h⁻¹ under optimized conditions.     

Catalytic alcoholysis of alkaline extracted lignin for the production of aromatic esters over SO42−/ZrO2-ATP

An efficient process for the depolymerization of alkaline extracted lignin (AEL) using attapulgite (ATP)-supported solid catalysts in ethanol was developed in this work. Different ATP-supported catalysts were prepared and used to catalyze the depolymerization of the lignin AEL. The results demonstrated that the addition of ATP-supported catalysts was favorable for controlling the distribution of valuable depolymerization products. The optimal solid catalyst SO₄²⁻/ZrO₂-ATP (Cat 2) exhibited high catalytic activity and selectivity, which showed a 78.6% conversion of AEL and a 29.4% selectivity to ethyl ferulate (ethyl 4-hydroxy-3-methoxycinnamate) with a catalyst/AEL ratio of 1 : 1 at 200 °C for 120 min. The catalyst could be reused and its catalytic activity did not obviously decreased after 6 successive runs. Particularly, a plausible mechanism involving esterification, hydrogenation, and dehydration for the production of aromatic esters from AEL depolymerization over SO₄²⁻/ZrO₂-ATP in ethanol was also proposed.

An efficient process for the depolymerization of alkaline extracted lignin (AEL) using attapulgite (ATP)-supported solid catalysts in ethanol was developed in this work.     

Palygorskite-anchored Pd complexes catalyze the coupling reactions of pyrimidin-2-yl sulfonates

In this work, an anchored Pd complex (PGS–APTES–Pd(OAc)₂) was prepared via simple and green steps from the natural clay mineral palygorskite and was well characterized by XPS, XRD, IR, SEM, and EDX. This complex was further utilized as a fine catalyst for the C–C/C–N coupling reactions of pyrimidin-2-yl sulfonates. Subsequently, the cyclic utilization test indicated the high stability and sustainability of this PGS–APTES–Pd(OAc)₂ catalyst, and no activation was required in the recycling process, providing an applicable and reusable catalyst in organic synthesis.

PGS–APTES–Pd(OAc)₂ was prepared through simple and green steps from the natural clay mineral palygorskite. Obviously, the stability and reusability of PGS–APTES–Pd(OAc)₂ were superior to those of the PGS–Pd catalyst (prepared by the impregnation method) in recycling test.     

Enhanced properties of Pd/CeO2-nanorods modified with alkaline-earth metals for catalytic oxidation of low-concentration methane

A series of Pd/CeO₂-nanorods catalysts modified with alkaline-earth metals were prepared by the incipient impregnation method. Their catalytic properties in low-concentration methane oxidation were also investigated. The catalysts were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and H₂-temperature-programmed reduction techniques. The catalytic results show that the Ca element doped in Pd/CeO₂, with optimum molar ratio of Pd to Ca of 2 and calcination temperature of 450 °C, improved the properties of the Pd-based catalyst remarkably, which is attributed to strong Pd–support interaction and high oxygen mobility. Therefore, calcium is more suitable as a promoter for enhancing the activities of the Pd/CeO₂ catalyst in methane oxidation.

A series of Pd/CeO₂-nanorods catalysts modified with alkaline-earth metals were prepared by the incipient impregnation method.     

Novel blended catalysts consisting of a TiO2 photocatalyst and an Al2O3 supported Pd–Au bimetallic catalyst for direct dehydrogenative cross-coupling between arenes and tetrahydrofuran

Dehydrogenative cross-coupling (DCC) is a clean methodology to make C–C bonds by using abundant C–H bonds. The blended catalyst, developed in this study, consists of a TiO₂ photocatalyst and an Al₂O₃ supported Pd–Au bimetallic catalyst and shows superior activity to the conventional TiO₂ photocatalyst loaded with the corresponding metal co-catalyst for the direct DCC between various arenes and tetrahydrofuran, with concomitant evolution of hydrogen gas. The reactions were done under mild conditions without consuming any oxidising agent or other additional chemicals. This new approach of separating the photocatalyst and the metal catalyst parts allows their independent modification to improve the overall catalytic performance.

A TiO₂ photocatalyst physically mixed with a supported Pd–Au bimetallic catalyst is more efficient than Pd loaded TiO₂ sample for the photocatalytic DCC between arene and THF.     

1,2,3-Triazole framework: a strategic structure for C–H⋯X hydrogen bonding and practical design of an effective Pd-catalyst for carbonylation and carbon–carbon bond formation

1,2,3-Triazole is an interesting N-heterocyclic framework which can act as both a hydrogen bond donor and metal chelator. In the present study, C–H hydrogen bonding of the 1,2,3-triazole ring was surveyed theoretically and the results showed a good agreement with the experimental observations. The click-modified magnetic nanocatalyst Pd@click-Fe₃O₄/chitosan was successfully prepared, in which the triazole moiety plays a dual role as both a strong linker and an excellent ligand and immobilizes the palladium species in the catalyst matrix. This nanostructure was well characterized and found to be an efficient catalyst for the CO gas-free formylation of aryl halides using formic acid (HCOOH) as the most convenient, inexpensive and environmentally friendly CO source. Here, the aryl halides are selectively converted to the corresponding aromatic aldehydes under mild reaction conditions and low Pd loading. The activity of this catalyst was also excellent in the Suzuki cross-coupling reaction of various aryl halides with phenylboronic acids in EtOH/H₂O (1 : 1) at room temperature. In addition, this catalyst was stable in the reaction media and could be magnetically separated and recovered several times.

The C–H hydrogen bonding of a 1,2,3-triazole framework was studied. An Fe₃O₄–chitosan core–shell incorporating a triazole/Pd complex was investigated as a nanocatalyst in carbonylation and C–C coupling.     

Pd catalyst supported on CeO2 nanotubes with enhanced structural stability toward oxidative carbonylation of phenol

Ordered CeO₂ nanotubes (CeO₂-T) were prepared via a hydrothermal synthesis process using the triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide (P123) as a morphology control agent. CeO₂-T characterization demonstrated the formation of single crystal structures having lengths between 1–3 μm and diameters < 100 nm. A supported Pd catalyst (Pd/CeO₂-T) was also prepared through hydrothermal means. H₂-temperature reduction profile and Raman spectroscopy analyses showed that the oxygen vacancies on the CeO₂ surface increased and the reduction temperature of the surface oxygen decreased after Pd loading onto CeO₂-T. Pd/CeO₂-T was employed as a catalyst toward the oxidative carbonylation of phenol and the reaction conditions were optimized. Phenol conversion was 53.2% with 96.7% selectivity to diphenyl carbonate under optimal conditions. The integrity of the tubular CeO₂ structure was maintained after the catalyst was recycled, however, both activity and selectivity significantly decreased, which was mainly attributed to the Pd active component significantly leaching during the reaction.

Schematic representation of formation of Pd/CeO₂-T.     

Two-step catalytic conversion of lignocellulose to alkanes

Direct conversion of lignocellulose to alkanes is challenged by the complex and recalcitrant nature of the starting material. Generally, alkanes are obtained from one of the main lignocellulose constituents (cellulose, hemicellulose or lignin) after their separation, and platform chemicals derived therein. Here we describe a two-step methodology, which uses unprocessed lignocellulose directly, targeting a mixture of alkanes. The first step involves the near-complete conversion of lignocellulose to alcohols, using a copper doped porous metal oxide (Cu-PMO) catalyst in supercritical methanol. The second step comprises a novel solvent exchange procedure and the exhaustive hydrodeoxygenation (HDO) of the complex mixture of aliphatic alcohols, obtained upon depolymerization, to C₂–C₁₀ alkanes by either HZSM-5 or Nafion at 180 °C in conjunction with Pd/C in dodecane. This describes an unprecedented two-step process from lignocellulose to hydrocarbons, with an overall carbon yield of 50%.

This work described a simple two-step process for the complete lignocellulose conversion to alkanes with high carbon yield.     

Palladium decorated on a new dendritic complex with nitrogen ligation grafted to graphene oxide: fabrication,characterization, and catalytic application

Immobilized Pd nanoparticles on a new ligand, namely, tris(pentaethylene-pentamine)triazine supported on graphene oxide (Pd_np-TPEPTA_(L)-GO) was introduced as a novel and robust heterogeneous catalyst for use in C–C bond formation reaction. The Pd_np-TPEPTA_(L)-GO catalyst was synthesized by complexation of Pd with TPEPTA as a ligand with high N-ligation sites that were supported on graphene oxide through 3-chloropropyltrimethoxysilane. The prepared catalyst was characterized using some microscopic and spectroscopic techniques. The TPEPTA_(L)-GO substrate is a 2D heterogeneous catalyst with a high specific surface area and a large amount of N-ligation sites. The Pd_np-TPEPTA_(L)-GO catalyst used in the C–C bond formation reaction between aryl or heteroaryl and phenylboronic acid derivatives was applied towards the synthesis of biaryl units in high isolated yields. Notably, a series of competing experiments were performed to establish the selectivity trends of the presented method. Also, this catalyst system was reusable at least six times without a significant decrease in its catalytic activity.

Immobilized Pd nanoparticles on a new ligand, namely, tris(pentaethylene-pentamine)triazine supported on graphene oxide (Pd_np-TPEPTA_(L)-GO) was introduced as a novel and robust heterogeneous catalyst for use in C–C bond formation reaction.     

Recyclable Pd/CuFe2O4 nanowires: a highly active catalyst for C–C couplings and synthesis of benzofuran derivatives

Pd/CuFe₂O₄ nanowire-catalyzed cross coupling transformations are described. Notably, these reactions showed excellent functional group tolerance. Further, the protocol is applied to a one-pot synthesis of benzofurans via a Sonogashira coupling and intramolecular etherification sequence. The catalyst was reused and found to maintain its activity and stability.

Efficient heterogeneous Pd/CuFe₂O₄ nanowires which catalyze cross coupling transformations are described. The protocol is applied to a one-pot synthesis of benzofurans via Sonogashira coupling and an intramolecular etherification sequence.     

Synthesis and characterization of a supported Pd complex on volcanic pumice laminates textured by cellulose for facilitating Suzuki–Miyaura cross-coupling reactions

Herein, a novel high-performance heterogeneous catalytic system made of volcanic pumice magnetic particles (VPMP), cellulose (CLS) natural polymeric texture, and palladium nanoparticles (Pd NPs) is presented. The introduced VPMP@CLS-Pd composite has been designed based on the principles of green chemistry, and suitably applied in the Suzuki–Miyaura cross-coupling reactions, as an efficient heterogeneous catalytic system. Concisely, the inherent magnetic property of VPMP (30 emu g⁻¹) provides a great possibility for separation of the catalyst particles from the reaction mixture with great ease. In addition, high heterogeneity and high structural stability are obtained by this composition resulting in remarkable recyclability (ten times successive use). As the main catalytic sites, palladium nanoparticles (Pd NPs) are finely distributed onto the VPMP@CLS structure. To catalyze the Suzuki–Miyaura cross-coupling reactions producing biphenyl pharmaceutical derivatives, the present Pd NPs were reduced from chemical state Pd²⁺ to Pd⁰. In this regard, a plausible mechanism is submitted in the context as well. As the main result of the performed analytical methods (including FT-IR, EDX, VSM, TGA, FESEM, TEM, BTE, and XPS), it is shown that the spherical-shaped nanoscale Pd particles have been well distributed onto the surfaces of the porous laminate-shaped VPMP. However, the novel designed VPMP@CLS-Pd catalyst is used for facilitating the synthetic reactions of biphenyls, and high reaction yields (∼98%) are obtained in a short reaction time (10 min) by using a small amount of catalytic system (0.01 g), under mild conditions (room temperature).

An efficient natural-based catalyst constructed of volcanic pumice, cellulose polymeric chains, and palladium nanoparticles is presented for Suzuki–Miyaura coupling reaction.     

Palladium supported on mixed-metal–organic framework (Co–Mn-MOF-74) for efficient catalytic oxidation of CO

Successful monometallic and bimetallic metal–organic frameworks with different Co/Mn ratios have been synthesized under solvothermal conditions. The as-synthesized MOFs followed by deposition of Pd nanoparticles with 0.5 to 7 wt%. The XRD, BET, SEM, TEM, EDAX and FT-IR characterization results reveal that bimetallic MOFs and Pd nanoparticles were finely dispersed on the prepared MOFs surfaces. XRD results confirm the formation of the desire MOFs and show the high degree of dispersion of Pd nanoparticles. TEM images show that Pd nanoparticles are nano-sized with almost uniform shape. EDAX shows that Pd nanoparticles successfully loaded on Co_0.5–Mn_0.5-MOF-74 catalyst. CO oxidation as a model reaction was then used to assess the catalytic performance of the prepared catalysts. The catalytic activity results show enhancement in the catalytic activities of monometallic MOFs after introducing another metal in the same framework and show an excellent improvement in CO conversion after loading with Pd nanoparticles. Furthermore, the samples that contain Pd nanoparticles exhibits higher catalytic activities which raised with increasing the content of Pd nanoparticles.

Pd nanoparticles were loaded on Co_x–Mn_(1−x)-MOF-74. 5 wt% Pd@Co_0.5–Mn_0.5-MOF-74 was the most effective catalyst for CO oxidation. The prepared catalysts displayed excellent stability during CO oxidation without significant decrease in catalytic performance.     

Lignin-first depolymerization of native corn stover with an unsupported MoS2 catalyst

The lignin-first biorefinery method appears to be an attractive approach to produce phenolic chemicals. Herein, corn stover was employed for the production of phenolic monomers using an unsupported non-noble MoS₂ catalyst. The yield of phenolic monomers was enhanced from 6.65% to 18.47% with MoS₂ at 250 °C and about 75% lignin was degraded with more than 90% glucan reserved in the solid residues. The Fourier-Transform Infrared (FT-IR) and heteronuclear single quantum coherence-nuclear magnetic resonance (¹H–¹³C HSQC-NMR) characterization suggested that the cleavage of the β-O-4, γ-ester and benzyl ether linkages were enhanced, promoting the delignification and the depolymerization of lignin. The catalyst performance was relatively effective with 14.30% phenolic monomer yield after the fifth run. The effects of the reaction temperature, the initial hydrogen pressure, the dosage of catalyst, and the reaction time were investigated. The model reactions were also proposed for the potential mechanism study. This work provides some basic information for the improvement of the graminaceous plant lignin-first process with a non-noble metal catalyst.

The non-noble metal catalyst MoS₂ played a positive role in the depolymerization of native corn stover lignin by lignin-first biorefinery.     

Facile route to synthesize Fe3O4@acacia–SO3H nanocomposite as a heterogeneous magnetic system for catalytic applications

In this work, a novel catalytic system for facilitating the organic multicomponent synthesis of 9-phenyl hexahydroacridine pharmaceutical derivatives is reported. Concisely, this catalyst was constructed from acacia gum (gum arabic) as a natural polymeric base, iron oxide magnetic nanoparticles (Fe₃O₄ NPs), and sulfone functional groups on the surface as the main active catalytic sites. Herein, a convenient preparation method for this nanoscale composite is introduced. Then, essential characterization methods such as various spectroscopic analyses and electron microscopy (EM) were performed on the fabricated nano-powder. The thermal stability and magnetic properties were also precisely monitored via thermogravimetric analysis (TGA) and vibrating-sample magnetometry (VSM) methods. Then, the performance of the presented catalytic system (Fe₃O₄@acacia–SO₃H) was further investigated in the referred organic reaction by using various derivatives of the components involved in the reaction. Optimization, mechanistic studies, and reusability screening were carried out for this efficient catalyst as well. Overall, remarkable reaction yields (94%) were obtained for the various produced derivatives of 9-phenyl hexahydroacridine in the indicated optimal conditions.

We designed and fabricated a novel catalytic system with high heterogeneity and magnetic features to facilitate the MCR synthetic reactions of 9-phenyl hexahydroacridine pharmaceutical derivatives.     

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.     

Production of liquid fuels from Kraft lignin over bimetallic Ni–Mo supported on ZIF-derived porous carbon catalyst

Non-noble bimetallic NiMo supported on zeolitic imidazolate framework-derived porous carbon (NiMo@FDC) catalyst for lignin depolymerization has been successfully developed. The synergism between Ni and Mo species in NiMo@FDC catalyst could promote the catalytic cleavage of C–O linkages in Kraft lignin. At a low reaction temperature of 240 °C and under 4 MPa H₂, the lignin liquefaction yield was 98.85 wt% and minimum coke yield was 1 wt%, particularly when using 10%NiMo@FDC catalyst. Additionally, at a high reaction temperature of 300 °C and under 2 MPa H₂, there was an overall yield of 86 wt% of liquid product and 42 wt% of petroleum ether soluble product. The higher heating value (HHV) increased from 27.65 MJ kg⁻¹ to 34.11 MJ kg⁻¹. In the cycling experiment, the bifunctional catalyst also demonstrated reversability and stability. The synergy of Ni hydrogenation sites and Mo coupled adsorption sites identified a possible mechanism path, which could offer considerable potential for lignin depolymerization.

The structure and synergy of NiMo@FDC catalyst have a significant effect on realizing the production of lignin-derived liquid fuels from Kraft lignin.     

Effect of polyvinylpyrrolidone (PVP) on palladium catalysts for direct synthesis of hydrogen peroxide from hydrogen and oxygen

When synthesizing nanoparticles in the liquid phase, polymeric materials (mainly polyvinylpyrrolidone, PVP) are applied as capping and/or stabilizing agents. The polymer layer on the nanoparticles must likely be removed since it blocks the active sites of the catalyst and inhibits mass transfer of the reactants. However, we have found that the polymer can have a positive effect on the direct synthesis of hydrogen peroxide. By testing Pd/SiO₂ catalysts with different amounts of PVP, it was revealed that an adequate amount of PVP resulted in a higher rate of hydrogen peroxide production (1001 mmol_H2O2 g_Pd⁻¹ h⁻¹) than pristine Pd/SiO₂ did (750 mmol_H2O2 g_Pd⁻¹ h⁻¹), unlike other PVP added Pd/SiO₂ catalysts containing excess PVP (less than 652 mmol_H2O2 g_Pd⁻¹ h⁻¹). The effect of PVP on the catalysts was examined by transmission electron microscopy, Fourier transform infrared spectroscopy, CO chemisorption, thermogravimetric analysis, and X-ray photoelectron spectroscopy. For the catalysts containing PVP, the oxidation state of the palladium 3d shifted to high binding energy due to electron transfer from Pd to the PVP molecules. Consequently, the presence of PVP on the catalysts inhibited oxygen dissociation and decomposition of the produced hydrogen peroxide, resulting in a high selectivity and high production rate of hydrogen peroxide.

Addition of polyvinylpyrrolidone to Pd/SiO₂ catalyst improved H₂O₂ selectivity by adjusting electronic state of palladium active species.     

Black phosphorous/palladium functionalized carbon aerogel nanocomposite for highly efficient ethanol electrooxidation

Direct ethanol fuel cells have great potential for practical power applications due to their easy operation, high energy density, and low toxicity. However, the slow and incomplete ethanol electrooxidation (EEO) reaction is a major drawback that hinders the development of this type of fuel cell. Here, we report a facile approach for the preparation of highly active, low cost and stable electrocatalysts based on palladium (Pd) nanoparticles and black phosphorus/palladium (BP/Pd) nanohybrids supported on a carbon aerogel (CA). The nanocomposites show remarkable catalytic performance and stability as anode electrocatalysts for EEO in an alkaline medium. A mass peak current density of 8376 mA mg_Pd⁻¹ is attained for EEO on the BP/Pd/CA catalyst, which is 11.4 times higher than that of the commercial Pd/C catalyst. To gain deep insight into the structure–property relationship associated with superior electroactivity, the catalysts are well characterized in terms of morphology, surface chemistry, and catalytic activity. It is found that the BP-doped CA support provides high catalyst dispersibility, protection against leaching, and modification of the electronic and catalytic properties of Pd, while the catalyst modifies CA into a more open and conductive structure. This synergistic interaction between the support and the catalyst improves the transport of active species and electrons at the electrode/electrolyte interface, leading to rapid EEO reaction kinetics.

A black phosphorus/palladium (BP/Pd) nanohybrid catalyst embedded in a carbon aerogel matrix exhibits remarkable electroactivity and durability for ethanol electrooxidation in an alkaline medium.