Synergistic Pt-WO3 Dual Active Sites to Boost Hydrogen Production from Ammonia Borane.
ABSTRACT: Development of synergistic heterogeneous catalysts with active sites working cooperatively has been a pursuit of chemists. Herein, we report for the first time the fabrication and manipulation of Pt-WO3 dual-active-sites to boost hydrogen generation from ammonia borane. A combination of DFT calculations, structural characterization, and kinetic (isotopic) analysis reveals that Pt and WO3 act as the active sites for ammonia borane and H2O activation, respectively. A trade-off between the promoting effect of WO3 and the negative effect of decreased Pt binding energy contributes to a volcano-shaped activity, and Pt/CNT-5W delivers a 4-fold increased activity of 710.1 molH2·molPt-1·min-1. Moreover, WO3 is suggested to simultaneously act as the sacrificial site that can divert B-containing by-products away from Pt sites against deactivation, yielding an increase from 24% to 68% of the initial activity after five cycles. The strategy demonstrated here could shed a new light on the design and manipulation of dual-active-site catalysts.
Project description:Supported metal clusters containing only a few atoms are of great interest. Progress has been made in synthesis of metal single-atom catalysts. However, precise synthesis of metal dimers on high-surface area support remains a grand challenge. Here, we show that Pt2 dimers can be fabricated with a bottom-up approach on graphene using atomic layer deposition, through proper nucleation sites creation, Pt1 single-atom deposition and attaching a secondary Pt atom selectively on the preliminary one. Scanning transmission electron microscopy, x-ray absorption spectroscopy, and theoretical calculations suggest that the Pt2 dimers are likely in the oxidized form of Pt2Ox. In hydrolytic dehydrogenation of ammonia borane, Pt2 dimers exhibit a high specific rate of 2800?molH2?molPt-1?min-1 at room temperature, ~17- and 45-fold higher than graphene supported Pt single atoms and nanoparticles, respectively. These findings open an avenue to bottom-up fabrication of supported atomically precise ultrafine metal clusters for practical applications.
Project description:Ammonia borane (NH3-BH3) is of interest as a hydrogen storage material because of its ease of use and its ability to release three molar equivalents of H2(g) via catalytic hydrolysis. Most heterogeneous catalysts for ammonia borane hydrolysis are nanoparticles containing expensive noble metals. Here, we show that metal ruthenate perovskites function as active and durable catalysts for ammonia borane hydrolysis. As a bulk powder, CaRuO3 catalyzes the hydrolysis of ammonia borane at room temperature and is recyclable and reusable. CaRuO3 facilitates the release of H2(g) from aqueous ammonia borane solutions at comparable rates to some other heterogeneous catalyst systems while having a low noble metal content. Other ruthenium-based perovskites, including SrRuO3, Ca2LaRuO6, Sr2CoRuO6, and SrLaCoRuO6, are similarly active catalysts for room-temperature ammonia borane hydrolysis.
Project description:Development of non-noble metal catalysts with similar activity and stability to noble metals is of significant importance in the conversion and utilization of clean energy. The catalytic hydrolysis of ammonia borane (AB) to produce 3 equiv. of H2, as an example of where noble metal catalysts significantly outperform their non-noble peers, serves as an excellent test site for the design and optimization of non-noble metal catalysts. Our kinetic isotopic effect measurements reveal, for the first time, that the kinetic key step of the hydrolysis is the activation of H2O. Deducibly, a transition metal with an optimal electronic structure that bonds H2O and -OH in intermediate strengths would favor the hydrolysis of AB. By employing a covalent triazine framework (CTF), a newly developed porous material capable of donating electrons through the lone pairs on N, the electron densities of nano-sized Co and Ni supported on CTF are markedly increased, as well as their catalytic activities. Specifically, Co/CTF exhibits a total turnover frequency of 42.3 molH2 molCo-1 min-1 at room temperature, which is superior to all peer non-noble metal catalysts ever reported and even comparable to some noble metal catalysts.
Project description:The development of highly-efficient heterogeneous supported catalysts for catalytic hydrolysis of ammonia borane to yield hydrogen is of significant importance considering the versatile usages of hydrogen. Herein, we reported the in situ synthesis of AgCo bimetallic nanoparticles supported on g-C?N? and concomitant hydrolysis of ammonia borane for hydrogen evolution at room temperature. The as-synthesized Ag0.1Co0.9/g-C?N? catalysts displayed the highest turnover frequency (TOF) value of 249.02 mol H?·(molAg·min)−1 for hydrogen evolution from the hydrolysis of ammonia borane, which was higher than many other reported values. Furthermore, the Ag0.1Co0.9/g-C?N? catalyst could be recycled during five consecutive runs. The study proves that Ag0.1Co0.9/g-C?N? is a potential catalytic material toward the hydrolysis of ammonia borane for hydrogen production.
Project description:A series of Cu@Pd/C with different Pd contents was prepared using the galvanic reduction method to disperse Pd on the surface of Cu nanoparticles on Cu/C. The dispersion of Pd was regulated by the Cu(I) on the surface, which was introduced by pulse oxidation. The Cu2O did not react during the galvanic reduction process and restricted the Pd atoms to a specific area. The pulse oxidation method was demonstrated to be an effective process to control the oxidization degree of Cu on Cu/C and then to govern the dispersion of Pd. The catalysts were characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscope (HRTEM), high angular annular dark field scanning TEM (HAADF-STEM), energy-dispersive spectroscopy (EDS) mapping, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), auger electron spectroscopy (AES), and inductively coupled plasma optical emission spectrometer (ICP-OES), which were used to catalyze the hydrogen evolution from ammonia borane. The Cu@Pd/C had much higher activity than the PdCu/C, which was prepared by the impregnation method. The TOF increased as the Cu2O in Cu/C used for the preparation of Cu@Pd/C increased, and the maximum TOF was 465 molH2 min-1 molPd-1 at 298 K on Cu@Pd0.5/C-640 (0.5 wt % of Pd, 640 mL of air was pulsed during the preparation of Cu/C-640). The activity could be maintained in five continuous processes, showing the strong stability of the catalysts.
Project description:Catalytic hydrolysis of ammonia borane (AB) has been considered as an effective and safe method to generate hydrogen. Development of highly active and low-cost catalysts is one of the key tasks for this technology. In this work, hexagonal CuCo₂O₄ nanoplatelets with a thickness of approximately 55 nm were prepared. In AB hydrolysis, those nanoplatelets exhibited ultrahigh catalytic activity with turnover frequency (TOF) of 73.4 molhydrogen min-1 molcat-1. As far as we know, this is one of the highest TOF values ever reported for non-noble metal catalysts. In addition, the effects of viscosity and different alkalis on the hydrolysis were also investigated. It is revealed that high viscosity of the reaction medium will retard the hydrolysis reaction. The presence of NaOH, KOH, and Na₂CO₃ in the reaction solution is favorable for hydrolytic process. In contrast, NH₃·H₂O will slow down the hydrolysis rate of ammonia borane. This work can provide some novel insight into the design of catalysts with both high performance and low cost. Besides, some findings in the present study can also offer us some information about how to improve the hydrolysis rates by optimizing the hydrolysis condition.
Project description:A galvanic replacement strategy has been successfully adopted to design Ag x Au1-x @CeO2 core@shell nanospheres derived from Ag@CeO2 ones. After etching using HAuCl4, the Ag core was in situ replaced with Ag x Au1-x alloy nanoframes, and void spaces were left under the CeO2 shell. Among the as-prepared Ag x Au1-x @CeO2 catalysts, Ag0.64Au0.36@CeO2 shows the optimal catalytic performance, whose catalytic efficiency reaches even 2.5 times higher than our previously reported Pt@CeO2 nanospheres in the catalytic reduction of 4-nitrophenol (4-NP) by ammonia borane (AB). Besides, Ag0.64Au0.36@CeO2 also exhibits a much lower 100% conversion temperature of 120 °C for catalytic CO oxidation compared with the other samples.
Project description:Production of hydrogen by catalytically hydrolyzing ammonia borane (AB) has attracted extensive attention in the field of catalysis and energy. However, it is still a challenge to develop a both inexpensive and active catalyst for AB hydrolysis. In this work, we designed a series of MoO?-doped MnCo?O? (x) catalysts, which were fabricated by a hydrothermal process. The morphology, crystalline structure, and chemical components of the catalysts were systematically analyzed. The catalytic behavior of the catalyst in AB hydrolysis was investigated. Among these catalysts, MoO?-doped MnCo?O? (0.10) microspheres composed of nanosheets exhibited the highest catalytic activity. The apparent activation energy is 34.24 kJ mol-1 and the corresponding turnover frequency is 26.4 molhydrogen min-1 molcat-1. Taking into consideration the low cost and high performance, the MoO?-doped MnCo?O? (0.10) microspheres composed of nanosheets represent a promising catalyst to hydrolyze AB for hydrogen production.
Project description:While thermolysis of ammonia-borane (AB) affords a mixture of aminoborane- and iminoborane oligomers, the most selective metal-based catalysts afford exclusively cyclic iminoborane trimer (borazine) and its B-N cross-linked oligomers (polyborazylene). This catalysed dehydrogenation sequence proceeds through a branched cyclic aminoborane oligomer assigned previously as trimeric B-(cyclodiborazanyl)amine-borane (BCDB). Herein we utilize multinuclear NMR spectroscopy and X-ray crystallography to show instead that this key intermediate is actually tetrameric B-(cyclotriborazanyl)amine-borane (BCTB) and a method is presented for its selective synthesis from AB. The reactivity of BCTB upon thermal treatment as well as catalytic dehydrogenation is studied and discussed with regard to facilitating the second dehydrogenation step in AB dehydrocoupling.
Project description:Herein, we have designed nonstoichiometric WO3, coupled with ZnCr layered double hydroxide (LDH) nanosheeet through Ag nanoparticle as the solid-state electron mediator to form WO3-X /Ag/ZnCr LDH Z-scheme photocatalyst. The presence of oxygen defect levels in as-synthesized materials was confirmed by Raman, X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) analyses. The photocatalytic performance of the catalysts was investigated by the tetracycline degradation and H2 energy production under visible light irradiation. The WO3-X /Ag/ZnCr LDH ternary heterostructure exhibits superior activity toward tetracycline degradation and hydrogen evolution. The excellent photocatalytic performance of the catalyst was attributed to the synergistic effects among three species (WO3-X , Ag, and ZnCr LDH) and the enhanced separation efficiency of photoinduced charge carriers through the Z-scheme WO3-X /Ag/ZnCr LDH system. In addition, the created oxygen deficiency on WO3-X could improve the photocatalytic behavior of ZnCr LDH in heterostructure by delaying the recombination efficiency of photoexcited electron-hole pairs. Furthermore, the higher affinity of tetracycline at the oxygen defect levels of the photocatalyst supports the high rate of tetracycline degradation. The enhanced photocatlytic activity of the catalysts was further supported by PL spectra and photoelectrochemical studies (electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) plot). The present research opens up a new strategy for designing highly efficient visible light-induced Z-scheme-based photocatalysts with high population of active sites for energy and environmental applications in a sustainable manner.