Rare Earth Elements(La,Ce,Pr)Modified Co/NC Catalyst for Efficient and Stable Ammonia Decomposition to Hydrogen Production

Co/NC catalysts modified with rare earth elements(La,Ce,Pr)were prepared by pyrolysis of rare earth elements doped ZIF-67.The experimental results show that the modification of rare earth elements significantly improves the ammonia decomposition activity and stability of the Co/NC catalyst.The La-Co/NC catalyst can achieve an 82.3%ammonia decomposition and 18.4 mmol hydrogen production rate at 550℃with a GHSV of 20000 cm^(3)·h^(-1).Furthermore,no obvious performance degradation is observed after 72 hours of reaction for all rare earth elements modified catalysts.It is shown that the modification of rare earth elements significantly improves the surface alkalinity and surface chemical state of the catalyst,and thus improves the ammonia decomposition activity of the catalyst.A new type of high-performance ammonia decomposition Co-based catalyst is proposed,and the promoting effect of rare earth elements on the activity of ammonia decomposition is revealed.

Integration of morphology and electronic structure modulation on cobalt phosphide nanosheets to boost photocatalytic hydrogen evolution from ammonia borane hydrolysis

The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.

Enhanced bimetallic CuCo nanoparticles on nitrogen-doped carbon for selective hydrogenation of furfural to furfuryl alcohol through strong electronic interactions

Bimetallic CuCo catalysts with different Cu to Co ratios on N-doped porous carbon materials(N-C)were achieved using impregnation method and applied in the hydrogenation of furfural(FAL)to furfuryl alcohol(FOL).The high hydrogenation activity of FAL over Cu_(1)Co_(1)/N-C was originated from the synergistic interactions of Cu and Co species,where Co^(0)and Cu^(0)simultaneously adsorb and activate H_(2),and Cu^(+) served as Lewis acid sites to activate C]O.Meanwhile,electrons transfer from Cu to Co promoted the formation of Cu^(+).In situ Fourier transform infrared spectroscopy analysis indicated that Cu_(1)Co_(1)/N-C adsorbed FAL with a tilted η^(1)-(O)configuration.The superior Cu_(1)Co_(1)/N-C showed excellent adsorbed ability towards H_(2) and FAL,but weak adsorption for FOL.Therefore,Cu_(1)Co_(1)/N-C possessed 93.1%FAL conversion and 99.0% FOL selectivity after 5 h reaction,which also exhibited satisfactory reusability in FAL hydrogenation for five cycles.

100 W-class green hydrogen production from ammonia at a dual-layer electrode containing a Pt-Ir catalyst for an alkaline electrolytic process

Ammonia allows storage and transport of hydrogen over long distances and is an attractive potential hydrogen carrier.Electrochemical decomposition has recently been used for the conversion of ammonia to hydrogen and is regarded as a future technology for production of CO_(2)-free pure hydrogen.Herein,a heterostructural Pt-Ir dual-layer electrode is developed and shown to achieve successful long-term operation in an ammonia electrolyzer with an anion exchange membrane(AEM).This electrolyzer consisted of eight membra ne electrode assemblies(MEAs)with a total geometric area of 200 cm~2 on the anode side,which resulted in a hydrogen production rate of 25 L h~(-1).We observed the degradation in MEA performance attributed to changes in the anode catalyst layer during hydrogen production via ammonia electrolysis.Furthermore,we demonstrated the relationship between the ammonia oxidation reaction(AOR)and the oxygen evolution reaction(OER).

20 ppm Anhydrous Ammonia Odor Agent Proposed for Hydrogen Fuel for Safe Detection of Leaks

Preferably 20 ppm anhydrous ammonia (NH3) is proposed to be added to hydrogen fuel (H) made from renewable energy sources (green hydrogen), so that H leaks may be easily detectable by smell, but not dangerously toxic. Including this odor agent, would allow H to be distributed safely in pipes, as required by law, and it would allow H to be safely stored, transported, and exported for sale, and widely commercialized. Further research is suggested to identify optimum pressure, temperature, and automated technique for injecting NH3 into H, and to chart the minimum concentration needed, as a function of temperature and humidity. An application to make hypersonic H burning aircraft safer for ground maintenance crews is proposed. An ability to make, store and distribute H, made from local sources of renewable energy, would reduce a need for fossil fuels, especially in poor, remote communities, where it could improve their economy by creating an export product for sale, while reducing pollution.

Hydrogen generation from ammonia electrolysis on bifunctional platinum nanocubes electrocatalysts

The ammonia electrolysis is a highly efficient and energy-saving method for ultra-pure hydrogen generation, which highly relies on electrocatalytic performance of electrocatalysts. In this work, high-quality platinum(Pt) nanocubes(Pt-NCs) with 4.5 nm size are achieved by facile hydrothermal synthesis. The physical morphology and structure of Pt-NCs are exhaustively characterized, revealing that Pt-NCs with special {100} facets have excellent uniformity, good dispersity and high crystallinity. Meanwhile, the electrocatalytic performance of Pt-NCs for ammonia electrolysis are carefully investigated in alkaline solutions, which display outstanding electroactivity and stability for both ammonia electrooxidation reaction(AEOR) and hydrogen evolution reaction(HER) in KOH solution. Furthermore, a symmetric Pt-NCs||Pt-NCs ammonia electrolyzer based on bifunctional Pt-NCs electrocatalyst is constructed, which only requires 0.68 V electrolysis voltage for hydrogen generation. Additionally, the symmetric Pt-NCs||Pt-NCs ammonia electrolyzer has excellent reversible switch capability for AEOR at anode and HER at cathode, showing outstanding alternating operation ability for ammonia electrolysis.

Ammonia borane-enabled hydrogen transfer processes:Insights into catalytic strategies and mechanisms

Transfer hydrogenation(TH) with in situ generated hydrogen donor is of great importance in reduction reactions, and an alternative strategy to traditional hydrogenation processes involving pressurized molecular hydrogen. Ammonia borane(NH3BH3, AB) is a promising material of hydrogen storage, and it has attracted much attention in reductive organic transformations owing to its high activity, good atom economy, nontoxicity, sustainability, and ease of transport and storage. This review focuses on summarizing the recent progress of AB-mediated TH reactions of diverse substrates including nitro compounds, nitriles, imines, alkenes, alkynes, carbonyl compounds(ketones and aldehydes), carbon dioxide,and N-and O-heterocycles. Syntheses protocols(metal-containing and metal-free), the effect of reaction parameters, product distribution, and variation of reactivity are surveyed, and the mechanism of each reaction involving the action mode of AB as well as structure-activity relationships is discussed in detail. Finally, perspectives are presented to highlight the challenges and opportunities for AB-enabled TH reactions of unsaturated compounds.

Ru surface density effect on ammonia synthesis activity and hydrogen poisoning of ceria-supported Ru catalysts

Evaluating the effect of metal surface density on catalytic performance is critical for designing high-activity metal-based catalysts.In this study,a series of ceria(CeCO_(2))-supported Ru catalysts(Ru/CeCO_(2))were prepared to analyze the effect of Ru surface density on the catalytic performance of Ru/CeCO_(2) for ammonia synthesis.For the Ru/CeCO_(2) catalysts with Ru surface densities lower than 0.68 Ru nm^(-2),the Ru layers were in close contact with CeCO_(2),and electrons were transferred directly from the CeCO_(2) defect sites to the Ru species.In such cases,the adsorption of hydrogen species on the Ru sites in the vicinity of 0 atoms was high,leading to a high ammonia synthesis activity and strong hydrogen poisoning.In contrast,the preferential aggregation of Ru species into large particles on top of the Ru overlayer resulted in the coexistence of Ru clusters and particles,for catalysts with a Ru surface density higher than 1.4 Ru nm^(-2),for which Ru particles were isolated from the direct electronic influence of CeCO_(2).Consequently,the Ru-Ceth interactions were weak,and hydrogen poisoning can be significantly alleviated.Overall,electron transfer and hydrogen adsorption synergistically affected the synthesis of ammonia over Ru/CeCO_(2) catalysts,and catalyst samples with a Ru surface density lower than 0.31 Ru nm^(-2) or exactly 2.1 Ru nm^(-2) exhibited high catalytic activity for ammonia synthesis.

Bimetallic RuM(M=Co,Ni)Alloy NPs Supported on MIL-110(AI):Synergetic Catalysis in Hydrolytic Dehydrogenation of Ammonia Borane

By adjusting various Ru/M （M=Co, Ni） molar ratios, a series of highly dispersed bimetallic RuM alloy nanoparticles （NPs） anchored on MIL-110（Al） have been successfully prepared via a conventional impregnation-reduction method. And they are first used as heterogeneous catalysts for the dehydrogenation reaction of AB at room temperature. The results reveal that the as-prepared RulCo1@MIL-110 and RulNi1@MIL-110 exhibit the highest catalytic activities in different RuCo and RuNi molar ratios, respectively. It is worthy of note that the turnover frequency （TOF） values of Ru1Co1@MIL-110 and Ru1Ni1@MIL-110 catalysts reached 488.1 and 417.1 mol H2 min-1 （mol Ru）-1 and the activation energies （Ea） are 31.7 and 36.0 k J/tool, respectively. The superior catalytic performance is attributed to the bimetallic synergistic action between Ru and M, uniform distribution of metal NPs as well as bi-functional effect between RuM alloy NPs and MIL-110. Moreover, these catalysts exhibit favorable stability after 5 consecutive cycles for the hydrolysis of AB.

Hydrogen generation from polyvinyl alcohol-contaminated wastewater by a process of supercritical water gasification

Gasification of polyvinyl alcohol （PVA）-contaminated wastewater in supercritical water （SCW） was investigated in a continuous flow reactor at 723-873 K, 20-36 MPa and residence time of 20-450 s. The gas and liquid products were analyzed by GC/TCD, and TOC analyzer. The main gas products were H2, CH4, CO and CO2. Pressure change had no significant influence on gasification efficiency. Higher temperature and longer residence time enhanced gasification efficiency, and lower temperature favored the production of H2. The effects of KOH catalyst on gas product composition were studied, and gasification efficiency were analyzed. The TOC removal efficiency （RTOC）, carbon gasification ratio （RCG） and hydrogen gasification ratio （RHG） were up to 96.00%, 95.92% and 126.40% at 873 K and 60 s, respectively, which suggests PVA can be completely gasified in SCW. The results indicate supercritical water gasification for hydrogen generation is a promising process for the treatment ofPVA wastewater.

Transition metal nanoparticles supported La-promoted MgO as catalysts for hydrogen production via catalytic decomposition of ammonia

The uniformly dispersed transition metal(Co, Ni and Fe) nanoparticles supported on the surface of La-promoted Mg O were prepared via a deposition-precipitation method for hydrogen production from catalytic decomposition of ammonia. X-ray diffraction, N2 adsorption-desorption, transmission electron microscopy, temperature-programmed reduction and temperature-programmed desorption were used to investigate the structure-activity relation of catalysts in NH3 decomposition. The results show that the strong interaction between active species and support can effectively prevent the active species from agglomerating during ammonia decomposition reaction. In addition, the introduction of La species not only facilitates the adsorption and decomposition of NH3 and desorption of N2, but also benefits the better dispersion of the active species. The prepared catalysts showed very high catalytic activity for ammonia decomposition compared with the same active composition samples that reported previously. Meanwhile, the catalysts showed excellent high-temperature stability and no any deactivation was observed, which are very promising candidates for the decomposition of ammonia to hydrogen.

Highly efficient and selective photocatalytic dehydrogenation of benzyl alcohol for simultaneous hydrogen and benzaldehyde production over Ni-decorated Zn_(0.5)Cd_(0.5)S solid solution

Photocatalytic conversion of solar energy into hydrogen and high value-added fine chemicals has attracted increasing attention. Herein, we demonstrate an efficient photocatalytic system for simultaneous hydrogen evolution and benzaldehyde production by dehydrogenation of benzyl alcohol over Nidecorated Zn_(0.5)Cd_(0.5)S solid solution under visible light. The photocatalytic system shows an excellent hydrogen production rate of 666.3 μmol h^(-1) with high stability. The optimal apparent quantum yield of52.5% is obtained at 420 nm. This noble-metal-free photocatalytic system displays much higher activity than pure Zn_(0.5)Cd_(0.5)S and Pt-loaded Zn_(0.5)Cd_(0.5)S solid solution. Further studies reveal that the metallic Ni nanocrystals play an important role in accelerating the separation of photogenerated charge carriers and the subsequent cleavage of α-C–H bond during dehydrogenation of benzyl alcohol.

Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol over An Ultrafine Co-B Amorphous Catalyst

A novel Co-B amorphous alloy catalyst in the form of ultrafine particles was prepared by chemical reduction of CoCl2 with aqueous NaBH4, which exhibited excellent activity and selectivity during the hydrogenation of cinnamaldehyde to cinnamyl alcohol in liquid phase. The optimum yield of cinnamyl alcohol was 87.6%, much better than the yield of using Raney Ni, Raney Co and other Co-based catalysts.

Biological removal of air loaded with a hydrogen sulfide and ammonia mixture

The nuisance impact of air pollutant emissions from wastewater pumping stations is a major issue of concern to China. Hydrogen sulfide and ammonia are commonly the primary odor and are important targets for removal. An alternative control technology, biofiltration, was studied. The aim of this study is to investigate the potential of unit systems packed with compost in terms of ammonia and hydrogen sulfide emissions treatment, and to establish optimal operating conditions for a full-scale conceptual design. The laboratory scale biofilter packed with compost was continuously supplied with hydrogen sulfide and ammonia gas mixtures. A volumetric load of less than 150 gH 2S/(m3·d) and 230 gNH 3/(m3·d) was applied for about fifteen weeks. Hydrogen sulfide and ammonia elimination occurred in the biofilter simultaneously. The removal efficiency, removal capacity and removal kinetics in the biofilter were studied. The hydrogen sulfide removal efficiency reached was very high above 99%, and ammonia removal efficiency was about 80%. Hydrogen sulfide was oxidized into sulphate. The ammonia oxidation products were nitrite and nitrate. Ammonia in the biofilter was mainly removed by adsorption onto the carrier material and by absorption into the water fraction of the carrier material. High percentages of hydrogen sulfide or ammonia were oxidized in the first section of the column. Through kinetics analysis, the presence of ammonia did not hinder the hydrogen sulfide removal. According to the relationship between pressure drop and gas velocity for the biofilter and Reynolds number, non-Darcy flow can be assumed to represent the flow in the medium.

Removal of Organic Matter and Ammonia Nitrogen in Azodicarbonamide Wastewater by a Combination of Power Ultrasound Radiation and Hydrogen Peroxide

A simple and efficient sonochemical method was developed for the degradation of organic matter and ammonia nitrogen in azodicarbonamide wastewater.The effects of initial pH,ultrasound format and peripheral water level on the sonolysis of hydrazine,urea,COD and ammonia nitrogen were investigated.It is found that the initial pH has a significant influence on the degradation of hydrazine and ammonia nitrogen,whereas this impact to urea is relatively small.It also shows that a noticeable enhancement of ammonia nitrogen removal could be achieved in a proper intermittent ultrasound operation mode,i.e.,1/1 min on/off mode.The height difference between the periph-eral water level and the inner water level of the flask affects the efficiency of ultrasonic treatment as well.

Photocatalytic selective oxidation of aromatic alcohols coupled with hydrogen evolution over CdS/WO_(3) composites

Simultaneously utilizing photogenerated electrons and holes to convert renewable biomass and its derivatives into corresponding value‐added products and hydrogen(H_(2))is a promising strategy to deal with the energy and environmental crisis.Herein,we report a facile hydrothermal method to construct a direct Z‐scheme CdS/WO_(3) binary composite for photocatalytic coupling redox reaction,simultaneously producing H_(2) and selectively converting aromatic alcohols into aromatic aldehydes in one pot.Compared with bare CdS and WO_(3),the CdS/WO_(3) binary composite exhibits significantly enhanced performance for this photocatalytic coupled redox reaction,which is ascribed to the ex‐tended light harvesting range,efficient charge carrier separation rate and optimized redox capabil‐ity of CdS/WO_(3) composite.Furthermore,the feasibility of converting various aromatic alcohols to corresponding aldehydes coupled with H_(2) evolution on the CdS/WO_(3) photocatalyst is proved and a reasonable reaction mechanism is proposed.It is hoped that this work can provide a new insight into the construction of direct Z‐scheme photocatalysts to effectively utilize the photogenerated electrons and holes for photocatalytic coupled redox reaction.

Interface electron collaborative migration of Co–Co3O4/carbon dots:Boosting the hydrolytic dehydrogenation of ammonia borane

Ammonia borane(AB)is an excellent candidate for the chemical storage of hydrogen.However,its practical utilization for hydrogen production is hindered by the need for expensive noble-metal-based catalysts.Herein,we report Co-Co3O4 nanoparticles(NPs)facilely deposited on carbon dots(CDs)as a highly efficient,robust,and noble-metal-free catalyst for the hydrolysis of AB.The incorporation of the multiinterfaces between Co,Co3O4 NPs,and CDs endows this hybrid material with excellent catalytic activity(rB=6816 mLH2 min^-1 gCo^-1)exceeding that of previous non-noble-metal NP systems and even that of some noble-metal NP systems.A further mechanistic study suggests that these interfacial interactions can affect the electronic structures of interfacial atoms and provide abundant adsorption sites for AB and water molecules,resulting in a low energy barrier for the activation of reactive molecules and thus substantial improvement of the catalytic rate.

Recovery of Hydrogen from Ammonia Plant Tail Gas by Absorption-Hydration Hybrid Method

In this work, the absorption-hydration hybrid method was used to recover （hydrogen ＋ nitrogen） from （hydrogen ＋ nitrogen ＋ methane ＋ argon） tail gas mixtures of synthetic ammonia plant through hydrate formation/dissociation. A high-pressure reactor with magnetic stirrer was used to study the separation efficiency. The in-fluences of the concentration of anti-agglomerant, temperature, pressure, initial gas-liquid volume ratio, and oil-water volume ratio on the separation efficiency were systematically investigated in the presence of tetrahydro-furan （THF）. Anti-agglomerant was used to disperse hydrate particles into the condensate phase for water-in-oil emulsion system. Since nitrogen is the material for ammonia production, the objective production in our separation process is （hydrogen ＋ nitrogen）. Our experimental results show that by adopting appropriate operating conditions, high concentration of （hydrogen ＋ nitrogen） can be obtained using the proposed technology based on forming hydrate.

Electron-enriched Pt induced by CoSe_(2)promoted bifunctional catalytic ability for low carbon alcohol fuel electro-reforming of hydrogen evolution

Alcohol fuel electro-reforming is promising for green hydrogen generation while developing efficient bifunctional catalysts for alcohol fuel electrolysis is still very tricky.Herein,we for the first time proposed the electron-enriched Pt induced by CoSe_(2)has an efficient bi-functional catalytic ability for alcohol fuels electro-reforming of hydrogen in acid electrolytes.The theoretical calculation revealed the advantages of electron-enriched Pt surface for the adsorption of intermediate,which is well supported by spectroscopic analysis and CO-stripping techniques.Largely improved catalytic performances of activity,durability,and kinetics are demonstrated compared to the conventional alloy system and commercial Pt/C catalyst,due to the efficient synergism of Pt and CoSe_(2);the peak current density of Pt/CoSe_(2)for methanol(ethanol)oxidation is 87.61(48.27)m A cm^(-2),which is about 3.3(2.0)times higher than that of Pt/C catalyst and 2.0(1.5)times that of the traditional PtCo alloy catalysts.Impressively,about 80%of the initial current was found after 1000 cycles of stability test for alcohol fuel oxidation of Pt/CoSe_(2)catalyst,higher than that of Pt/C(ca.50%)and PtCo catalyst(65%).When Pt/CoSe_(2)catalyst serviced as bi-functional catalysts for electrolyzer,a low cell potential of 0.65(0.78)V for methanol(ethanol)electrolysis was required to reach 10 m A cm^(-2),which was about 1030(900)m V less than that of conventional water electrolysis using Pt/C as the catalyst.The current result is instructive for the design of novel bifunctional catalyst and the understanding of hydrogen generation via alcohol fuel electro-reforming.

Carbon dots-confined CoP-CoO nanoheterostructure with strong interfacial synergy triggered the robust hydrogen evolution from ammonia borane

Ammonia borane(NH_(3)BH_(3),AB) is promising for chemical hydrogen sto rage;however,current systems for rapid hydrogen production are limited by the expensive noble metal catalysts required for AB hydrolysis.Here we report the design and synthesis of a highly efficient and robust non-noble-metal catalyst for the hydrolysis of AB at 298 K(TOF=89.56 molH_(2) min^(-1) molCo^(-1)).Experiments and density functional theory calculations were performed to explore the catalyst’s hybrid nanoparticle heterostructure and its catalytic mechanism.The catalyst comprised nitrogen-doped carbon dots confining CoO and CoP,and exhibited strong interface-induced synergistic catalysis for AB hydrolysis that effectively decreased the energy barriers for the dissociation of both AB and water molecules.The co-doping of N and P introduced numerous defects,and further regulated the reactivity of the carbon layers.The heterogeneous interface design technique presented here provides a new strategy for developing efficient and inexpensive non-noblemetal catalysts that may be applicable in other fields related to energy catalysis.