Pd Nanocatalysts Research Articles

Nitrogen-Rich Porous Organic Polymers from an Irreversible Amine-Epoxy Reaction for Pd Nanocatalyst Carrier.

Nitrogen-rich porous organic polymers were fabricated through a nonreversible ring-opening reaction from polyamines and polyepoxides (PAEs). The epoxide groups reacted with both primary and secondary amines provided by the polyamines at different epoxide/amine ratios with polyethylene glycol as the solvent to form the porous materials. Fourier-transform infrared spectroscopy confirmed the occurrence of ring opening between the polyamines and polyepoxides. The porous structure of the materials was confirmed through N2 adsorption-desorption data and scanning electron microscopy images. The polymers were found to possess both crystalline and noncrystalline structures, as evidenced by X-ray diffraction and high-resolution transmission electron microscopy (HR-TEM) results. The HR-TEM images revealed a thin, sheet-like layered structure with ordered orientations, and the lattice fringe spacing measured from these images was consistent with the interlayer of the PAEs. Additionally, the selected area electron diffraction pattern indicated that the PAEs contained a hexagonal crystal structure. The Pd catalyst was fabricated in situ onto the PAEs support by the NaBH₄ reduction of the Au precursor, and the size of the nano-Pd was about 6.9 nm. The high nitrogen content of the polymer backbone combined with Pd noble nanometals resulted in excellent catalytic performance in the reduction of 4-nitrophenol to 4-aminophenol.

Chitosan derived efficient and stable Pd nano-catalyst for high efficiency hydrogenation

The design and development of green and efficient supported catalysts is the frontier direction in the field of green synthesis, which conforms to the strategic concept of green sustainable chemistry and “carbon neutrality”. Herein, we used a renewable resource chitosan (CS) derived from seafood wastes of chitin as carriers to design two different chitosan-supported palladium (Pd) nano-catalysts through different activation methods. The Pd particles were firmly and uniformly dispersed on the chitosan microspheres due to the interconnected nanoporous structure and functional groups of chitosan, proved by diverse characterizations. The chitosan supported catalysts (Pd@CS) was applied to hydrogenation of 4-nitrophenol, which showed competitive catalytic activity compared to commercial Pd/C, un-supported nano-Pd and Pd(OAc)2 catalysts, as well as excellent catalytic activity, good reusability, long-life and broad applicability in selective hydrogenation of aromatic aldehydes, suggesting potential of applications in green industrial catalysis.

Electrochemical Synthesis of Rh Nanorods with High-Index Facets for the Oxidation of Formic Acid

Noble metal catalysts play an important role in developing efficient fuel cells for commercial application at a large scale. Among them, Pt-group metal nanocatalysts enclosed with high-index facets have been expected to exhibit high electrocatalytic activity due to the high density of the low-coordination step and kink atoms exposed on the surface. Many good studies on Pt and Pd nanocatalysts enclosed with high-index facets have been reported while Rh nanocatalysts with a high-index facet have rarely been prepared. In this work, Rh nanorods with high-index facets (310) were synthesized successfully through repeated oxygenated species adsorption/desorption mediated by square wave potential (SWP). Electrochemical tests showed that Rh nanorods with high-index facets exhibited excellent electrocatalytic activity for the formic acid oxidation reaction (FAOR), and the peak current densities in positive scan of Rh nanorods (4.48 mA·cm–2) was 4.7 times higher than that of Rh black catalysts (0.95 mA·cm–2). In addition, the Rh nanorods could maintain higher current density than that of the Rh black catalysts throughout the time domain with potential held at 0.45 V, indicating that Rh nanorods had good stability for FAOR. The enhanced electrocatalytic performance of the Rh nanorods could be mainly ascribed to high-index facets with step and kink atoms, which could provide sufficient active sites for FAOR.

Rational Utilization of Black Phosphorus Nanosheets to Enhance Palladium-Mediated Bioorthogonal Catalytic Activity for Activation of Therapeutics.

Pd-catalyzed chemistry has played a significant role in the growing subfield of bioorthogonal catalysis. However, rationally designing Pd nanocatalysts that show outstanding catalytic activity and good biocompatibility poses a great challenge. Herein, we propose an innovative strategy through exploiting black phosphorous nanosheets (BPNSs) to enhance Pd-mediated bioorthogonal catalytic activity. Firstly, the electron-donor properties of BPNSs enable in situ growth of Pd nanoparticles (PdNPs) on it. Meanwhile, due to the superb capability of reducing PdII , BPNSs can act as hard nucleophiles to accelerate the transmetallation in the decaging reaction process. Secondly, the lone pair electrons of BPNSs can firmly anchor PdNPs on their surface via Pd-P bonds. This design endows Pd/BP with the capability to retard tumor growth by activating prodrugs. This work proposes new insights into the design of heterogeneous transition-metal catalysts (TMCs) for bioorthogonal catalysis.

Rational Utilization of Black Phosphorus Nanosheets to Enhance Palladium‐Mediated Bioorthogonal Catalytic Activity for Activation of Therapeutics

AbstractPd‐catalyzed chemistry has played a significant role in the growing subfield of bioorthogonal catalysis. However, rationally designing Pd nanocatalysts that show outstanding catalytic activity and good biocompatibility poses a great challenge. Herein, we propose an innovative strategy through exploiting black phosphorous nanosheets (BPNSs) to enhance Pd‐mediated bioorthogonal catalytic activity. Firstly, the electron‐donor properties of BPNSs enable in situ growth of Pd nanoparticles (PdNPs) on it. Meanwhile, due to the superb capability of reducing PdII, BPNSs can act as hard nucleophiles to accelerate the transmetallation in the decaging reaction process. Secondly, the lone pair electrons of BPNSs can firmly anchor PdNPs on their surface via Pd−P bonds. This design endows Pd/BP with the capability to retard tumor growth by activating prodrugs. This work proposes new insights into the design of heterogeneous transition‐metal catalysts (TMCs) for bioorthogonal catalysis.

Effects of Palladium Precursors on the Activity of Palladium Nanocatalysts for the Oxidation of Volatile Organic Components.

To screen a suitable precursor, the effects of palladium salts on performance of Pd nanocatalysts for the oxidation of volatile organic components (VOCs) were investigated. A series of catalysts was prepared by impregnating Pd(NO3)2, PdCl2 and Pd(NH3)4Cl2 on alumina-coated cordierites. These catalysts were characterized by XRF, ICP-OES, XRD, N2 adsorption-desorption, TEM, EDS, Raman spectroscopy, pulse-CO chemisorption, H2-TPR, NH3-TPD, and XPS. Pulse-CO chemisorption and TEM showed that Pd species formed by Pd(NO3)2 have the highest metal dispersion (17.7%), while the other two were aggregating. For the same Pd loading, the higher the metal dispersion, the more the number of PdO species, so the number of PdO particles in the catalyst prepared from Pd (NO3) 2 is the largest. The catalytic oxidation activities of these catalysts were evaluated by ethane and propane. Based on a 99% conversion in the oxidation of ethane and propane at 598 K and 583 K, respectively, the catalyst prepared from Pd(NO3)2 was considered to be the best performing catalyst. The chloride species in precursors can promote the aggregation of Pd species and poison the catalysts. The results show that Pd(NO3)2 is more suitable as the precursor of VOC oxidation catalyst than PdCl2 and Pd(NH3)4Cl2.

Efficient liquid-phase hydrogenation of bromate over nanosized Pd catalysts supported on TpBD-Me2 covalent organic framework

The formation of toxic and carcinogenic bromate, BrO3–, during the disinfection of fresh or seawater by ozonation poses a threat to the human health, and therefore the development of methodologies for its removal from water is of high importance. Heterocatalytic bromate hydrogenation has been widely employed to decrease the BrO3– ion concentration in water below the strict legal limit imposed. In this work, we evaluate for the first time the performance of a covalent organic framework (COF) for this reaction. TpBD-Me2 COF was synthesized on gram scale and used as both catalyst and support for Pd nanocatalysts with different Pd loadings for bromate hydrogenation reaction.TpBD-Me2 was found to present considerable catalytic activity for BrO3– reduction with 60% conversion after 180 min. The conversion increased with increasing Pd loading of the COF, with the sample with 5% Pd on COF reaching 93% conversion after 180 min. The catalytic activity was further improved by performing an in situ pre-reduction step before the reaction, resulting in complete conversion of BrO3– already after 60 min of reaction. These results show that COF materials are efficient catalysts for this application.

Tungsten(VI) oxide as a versatile support for Pd nanocatalysts for alkaline direct alcohol fuel cells

The instability of carbon support materials has motivated the development of metal oxides supports which are stable under the fuel cell environment. In this study, tungsten (VI) oxide (WO3) is utilized as a secondary support and cocatalyst for the electrooxidation of methanol and ethanol. Functionalized carbon nanodots employed as primary supports were blended with WO3 nanoparticles to form a composite support onto which Pd nanoparticles were deposited by a borohydride reduction method. The synthesized Pd/fCNDs-WO3 electrocatalysts were characterized by Transmission Electron microscopy (TEM), X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy. XRD results proved that incorporating WO3 into Pd/fCNDs electrocatalyst shifts the Pd diffraction peaks to lower 2Ɵ value due to lattice relaxation. XPS results revealed that W exist in oxidised form and confirmed the strong interaction between the support material and the catalyst. The Pd/fCNDs-WO3 electrocatalysts exhibited a remarkable catalytic activity towards methanol and ethanol oxidation. High current densities of 87.24 mA cm−2 and 44.23 mA cm−2 were obtained for ethanol and methanol oxidation, respectively, using a catalyst with 2.5% Pd loading. EIS, CA and stability tests revealed that the presence of WO3 in Pd/fCNDs electrocatalyst improves the kinetics, tolerance to poisoning and long-term durability in alkaline conditions. This superior performance is attributed to the electronic coupling between Pd and WO3 nanoparticles.

Magnetic bentonite decorated with Pd nanoparticles and cross-linked polyvinyl pyridine as an efficient nanocatalyst for Suzuki coupling and 4-Nitrophenol reduction reactions

This study reports the preparation of a novel type of support based on magnetically recyclable bentonite functionalized with divinylbenzene-polyvinyl pyridine (PVP-DVB) for Pd (II) nanocatalyst by a simple cost-effective method. Firstly, the conventional co-precipitation method synthesized Fe3O4 nanoparticles (NPs) onto bentonite sheets. Then the prepared magnetic support surface was functionalized by divinylbenzene-polyvinyl pyridine (PVP-DVB) to create a cross-linked polymer with a high coordination ability with palladium. Repeated nitrogen units in the PVP-DVB polymer chain increase the number of Pd bonds and thus lead to higher performance of the nanocatalyst. Finally, the palladium NPs were simultaneously synthesized and immobilized under mild conditions. The synthesized nanocatalyst was characterized by several methods such as scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, vibrating sample magnetometer, inductively coupled plasma mass spectrometry and thermogravimetric analysis. The efficiency of synthesized heterogeneous nanocatalyst was investigated in Suzuki–Miyaura cross-coupling reactions between a range of aryl halides (X = Cl, Br, I) with phenylboronic acid and in the reduction of 4-nitrophenol (4-NP). Moreover, the synthesized nanocatalyst could be easily recovered and reused several times with an efficiency greater than 90%.

Ultrafiltration Pd-immobilized catalytic membrane microreactors continuously reduce nitrophenol: A study of catalytic activity and simultaneous separation

Catalytic membrane microreactors (CMMRs) are an exciting new technology that combine catalysis with membranes by seeding the high internal surface area of membranes with catalysts. This enables the continuous purification and production of organic compounds with high catalytic activity, while maintaining nanocatalyst size and stability. This study reports a simple two-step batch reaction approach for synthesizing stable Pd-immobilized catalytic membranes to transform 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in a flow-through CMMR system. The product (4-AP) is an essential intermediate for the polymer and solvent chemical industry. Pd-immobilized membranes exhibited strong catalytic activity for 4-NP reduction in the presence of NaBH4, with 4-fold higher reduction (79.7%) and 2-fold higher reduction rate (1.08 mol m−2h−1) as compared to control membranes without catalysts. The catalytic mechanisms were elucidated, such that the catalytic reduction processes were conducted via a sequential hydrogenation reaction where Pd nanocatalysts facilitated H* transfer from BH4- to 4-NP. Ultimately, the 4-AP product was gradually desorbed from the catalytic sites, achieving continuous reduction with high reduction efficiency. Furthermore, by combing ultrafiltration and catalysis, Pd-immobilized membranes showed >99% of 4-NP conversion and >90% of 1 MDa PEO rejection, demonstrating a great potential to be applied in high-efficient wastewater treatment processes.

Palladium doped with boron and phosphorus on activated carbon: a high-performance nanocatalyst for the hydrogenation of alkenes

Fabrication of high-performance palladium on activated carbon (Pd/AC) nanocatalysts for hydrogenation of alkenes to reduce the cost of reaction products has always been of interest to researchers and industries. Herein, the purpose was the step-by-step investigation of the simple precipitation-reduction method to determine the best chemicals usable in producing the high-performance 10%Pd/AC nanocatalyst for the hydrogenation of alkenes. Hence, different types of carbon supports, alkaline agents, and reducing agents were selected for this purpose. Catalytic hydrogenation of cinnamic acid to hydrocinnamic acid was used as a well-known standard test for evaluating the activity of the nanocatalysts. The AC prepared by pine wood, H2PdCl4, KHCO3, and NaBH4/NaH2PO2 were the most suitable materials for producing high-performance Pd/AC using the mentioned method. It was specified that activity is increased with the lower amount of oxygenated acidic functional groups on the AC, greater cation radius of the alkaline agent, weaker alkaline agent, and higher reduction power of the reducing agent. NaH2PO2 and especially NaBH4 increase the activity more than other reducing agents because of their high reduction power and adding phosphorus (P) and boron (B) to Pd, respectively. Three nanocatalysts with the most activity were chosen for more investigations by different analyses. The results of these analyses were according to the procedure obtained for their catalytic activity. The reusability test of chosen nanocatalysts indicated that the stability of Pd/AC is increased by doping the Pd with B and especially P. According to the obtained results, Pd nanocatalyst doped with both P and B is strongly recommended for application in alkenes hydrogenation.

A PPh3 modified-chitosan supported Pd nanocatalyst for heterogeneous Suzuki–Miyaura cross coupling reactions

A PPh3 modified-chitosan supported Pd nanocatalyst has been developed for heterogeneous Suzuki–Miyaura cross coupling reactions with high catalytic activity, wide substrate compatibility and good recyclability.

Pd nanocatalysts adsorbed onto silica nanoparticle coated indium tin oxide: a reusable nanozyme for glucose detection.

Nanozymes are nanomaterials that exhibit enzyme-like activity upon exposure to a substrate solution. The use of noble and platinum group metals enhances enzyme-like catalytic activity. However, noble metals are obtained at a high cost; therefore, their recovery after use is of high importance. Herein, we report the fabrication of indium tin oxide-silica nanoparticles decorated with palladium nanoparticles (ITO-SiO2-prS-PdNPs). The ITO-SiO2-prS-PdNPs were evaluated for peroxidase-like activity toward the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2. A colour change from clear or colourless TMB to blue colour (oxidized TMB products) was observed confirming the peroxidase-like activity. A typical Michaelis-Menten enzyme-like behaviour is observed with Km values of 0.68 mM for H2O2 and 0.47 mM for TMB, which are better than the reported values for horse-radish peroxidase (HRP) for the same substrate. The peroxidase-like activity of ITO-SiO2-prS-PdNPs was found to proceed via the electron-transfer mechanism. The ITO-SiO2-prS-PdNPs were cleaned successfully after each use by rinsing with water and ethanol solution thus making the surface simple and easy to recover and reuse. A reusable and highly selective colorimetric assay for glucose detection based on the peroxidase-like activity of ITO-SiO2-prS-PdNPs gave excellent results. ITO-SiO2-prS-PdNPs exhibited a good linear range of 5.0-30 μM, a low limit of detection (LOD) of 1.84 μM and a limit of quantification (LOQ) of 6.14 μM. Finally, the nanozyme (ITO-SiO2-prS-PdNPs) was successfully used to detect glucose in a complex newborn calf serum (NCS), representing a real sample.

Inserting Single-Atom Zn by Tannic Acid Confinement To Regulate the Selectivity of Pd Nanocatalysts for Hydrogenation Reactions.

Precisely controlling the selectivity of nanocatalysts has always been a hot topic in heterogeneous catalysis but remains difficult owing to their complex and inhomogeneous catalytic sites. Herein, an effective strategy to regulate the chemoselectivity of Pd nanocatalysts for selective hydrogenation reactions by inserting single-atom Zn into Pd nanoparticles is reported. Taking advantage of the tannic acid coating-confinement strategy, small-sized Pd nanoparticles with inserted single-atom Zn are obtained on the O-doped carbon-coated alumina. Compared with the pure Pd nanocatalyst, the Pd nanocatalyst with single-atom Zn insertion exhibits prominent selectivity for the hydrogenation of p-iodonitrobenzene to afford the hydrodeiodination product instead of nitro hydrogenation ones. Further computational studies reveal that the single-atom Zn on Pd nanoparticles strengthens the adsorption of the nitro group to avoid its reduction and increases the d-band center of Pd atoms to facilitate the reduction of the iodo group, which leads to enhanced selectivity. This work provides new guidelines to tune the selectivity of nanocatalysts with guest single-atom sites.

Efficient Construction of Symmetrical Diaryl Sulfides via a Supported Pd Nanocatalyst-Catalyzed C-S Coupling Reaction

Aryl sulfides play an important role in pharmaceuticals, biologically active molecules and polymeric materials. Herein, a general and efficient protocol for Pd@COF-TB (a kind of Pd nanocatalyst supported by a covalent organic framework)/DIPEA-catalyzed one-pot synthesis of symmetrical diaryl sulfides through a C-S coupling reaction from aryl iodides and Na2S2O3 is developed. More importantly, the addition of N,N-diisopropylethylamine (DIPEA) can not only enhance the catalytic activity of a Pd@COF-TB nanocatalyst, but also effectively inhibit the formation of biphenyl byproducts, which are a product of Ullmann reaction. Besides, it has been confirmed that the aryl Bunte salts generated in situ from Na2S2O3 and aryl iodides are the sulfur sources involved in this C-S coupling reaction. With the strategy proposed in this work, a variety of symmetrical diaryl sulfides could be obtained in moderate to excellent yields with a high tolerance of various functional groups. Moreover, a possible mechanism of this Pd nanoparticle-catalyzed C-S coupling reaction is proposed based on the results of controlling experiments.

Bilayer MXene‐Derived Carbon‐Encapsulated Palladium Nanocatalysts: Engineering Robust Electronic and Chemical Interfaces for Oxygen Reduction and Zinc–Air Batteries

AbstractDesigning highly active and durable electrocatalysts remain an ongoing challenge in the oxygen reduction reaction (ORR). Here, the reductive IL/Ti3C2Tx(FA) is produced in a water‐free mixture of formic acid (FA), ionic liquid (IL) and LiF, subsequently, the simultaneous reduction encapsulation trap the Pd nanocatalysts and IL within bilayer carbide‐derived carbon (CDC) to obtain Pd@IL/CDC(FA) with high metal loading up to 69.7%. Thereby, the featured active phases in Pd@IL/CDC(FA) impart potent chemical nanoconfinement to defend metals from dissolution and aggregation, boost mass and electron transfer, and mediate oxidation states and adsorption/desorption of metal Pd in the ORR. Instead of deactivation and Ostwald ripening, the catalytic performances of Pd@IL/CDC(FA) are gradually enhanced in an accelerated durability test up to 20 000 cycles. In a Zn–air battery, the Pd@IL/CDC(FA) cathode gives a specific capacity of 812.6 mAh gZn−1 and a voltage loss of only 41 mV in galvanostatic discharge for 1000 h. The work opens new venues in controllably preparing high activity and durable electrocatalysts from in‐situ generated CDCs.

Turning the Tide on Pollution with Nano catalysts: From Breaking Down Harmful Emissions to Recycling CO2

the decomposition of harmful emissions and recycling of CO2 into useful products. The work covered herein envelops synthesis, characterization, and evaluation of various nano catalysts such as TiO2, ZnO, Fe2O3, Au, Pt, Pd, and an Au-Pd nano alloy. These were synthesized by different preparation techniques, especially the sol-gel and hydrothermal methods, while their structural and surface properties were characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and BET surface area analysis. The catalytic performances of the prepared nanomaterials were performed against the degradation of NOx, SOx, and VOCs and in the conversion of CO2 into methanol, ethanol, and hydrocarbons. The results obtained showed that nano catalysts did a tremendous job in controlling emissions through the decomposition of up to 95% of VOCs, while Pd-nano catalysts proved efficient enough in CO2 conversion, yielding up to 82% hydrocarbon products. Without doubt, the obtained results prove that nano catalysts bear huge potential to solve all environmental problems across the globe

Alloying Iron into Palladium Nanoparticles for an Efficient Catalyst in Acetylene Dicarbonylation.

Motivated by the prominent catalytic performance and durability of nanoalloy catalysts, the Pd-based bimetallic nanoalloy catalysts were prepared using an aqueous reduction method. The Fe-Pd bimetallic nanoalloy catalyst (nano-Fe/Pd) demonstrated 98.4% yield and 99.7% selectivity for the unsaturated 1,4-dicarboxylic acid diesters. Moreover, the inductively coupled plasma (ICP) analysis shows that the Pd leaching of the catalyst can be effectively suppressed by alloying Fe atoms into the Pd crystal lattice for acetylene dicarbonylation. The detailed catalyst structure and morphology characterization demonstrate that introducing Fe into the Pd nanoparticles tunes the electronic-geometrical properties of the catalyst. Theoretical calculations indicate that the electrons of Fe transfer to Pd in the nano-Fe/Pd catalyst, enhancing activation of the C≡C bond in acetylene and weakening CO absorption capacity on catalyst surfaces. Alloying Fe into the Pd nanocatalyst effectively inhibits active metal leaching and improves catalyst activity and stability under high-pressure CO reactions.

Computational Insights into Ru, Pd and Pt fcc Nano-Catalysts from Density Functional Theory Calculations: The Influence of Long-Range Dispersion Corrections

Ruthenium, palladium and platinum fall within the group of noble metals that are widely used in catalysis, especially for the electrocatalytic production of hydrogen. The dominant phase of the bulk Ru metal is hexagonal close-packed (hcp), which has been studied extensively. However, significantly less attention has been paid to the face-centred cubic (fcc) phases, which have been observed in nanoparticles. In this study, we have carried out density functional theory calculations with long-range dispersion corrections [DFT-D2, DFT-D3 and DFT-D3-(BJ)] to investigate the lattice parameters, surface energies and work functions of the (001), (011) and (111) surfaces of Ru, Pd and Pt in the fcc phase. When investigating the surface properties of the three metals, we observed that the DFT-D2 method generally underestimated the lattice parameters by up to 2.2% for Pt and 2.8% for Ru. The surface energies followed the observed trend (111) < (001) < (011) for both Ru and Pd with all three methods, which is comparable to experimental data. For Pt the same trend was observed with DFT-D2 and DFT-D3(BJ), but it deviated to Pt (111) < Pt (011) < Pt (001) for the DFT-D3 method. DFT-D2 overestimated the surface energies for all three Miller Indexes by 82%, 73%, and 60%, when compared to experimental values. The best correlation for the surface energies was obtained with the DFT-D3 and DFT-D3(BJ) methods, both of which have deviate by less than 15% deviation for all surfaces with respect to experiment. The work function followed the trend of Φ (111) < Φ (001) < Φ (011) for all three metals and calculated by all three methods. Five different types of Ru, Pd and Pt nanoparticles were considered, including icosahedral, decahedral, cuboctahedral, cubic and spherical particles of different sizes. The bulk, surface and nanoparticle calculations showed that the DFT-D2 method for Pt overestimated the exchange-correlation, leading to higher energy values that can be contributed erroneously to a more stable structure. The calculations showed that as soon as the surface-to-bulk ratio > 1, the energy per atom resembles bulk energy values.

Amine-functionalized hierarchically porous carbon supported Pd nanocatalysts for highly efficient H2 generation from formic acid with fast-diffusion channels

Formic acid (FA) has come to be considered a potential candidate for hydrogen storage, and the development of efficient catalysts for H2 releasing is crucial for realizing the sustainable process from FA. Herein, we have developed the ultrafine Pd nanoparticle (NPs) with amine-functionalized carbon as a support, which was found to show an excellent catalytic activity in H2 generation from FA dehydrogenation. The synergetic mechanism between amine-group and Pd active site was demonstrated to facilitate H2 generation by β-hydride elimination. Moreover, the texture of support for Pd NPs also plays an important role in determining the reactivity of FA, since the diffusion of gaseous products makes the kinetics of diffusion as a challenge in this high performance Pd catalysts. As a result, the as-prepared Pd/NH2-TPC catalyst with the small sized Pd nanoparticles and the hierarchically porous structures shows a turnover of frequency (TOF) value of 4312 h−1 for the additive-free FA dehydrogenation at room temperature, which is comparable to the most promising heterogeneous catalysts. Our results demonstrated that the intrinsic catalytic activities of active site as well as the porous structure of support are both important factors in determining catalytic performances in H2 generation from FA dehydrogenation, which is also helpful to develop high-activity catalysts for other advanced gas-liquid-solid reactions systems.