Photocatalytic reduction of dinitrogen to ammonia over noble-metal-loaded TiO2
TL;DR: The photocatalytic reduction of dinitrogen to ammonia is influenced by the nature and amount of metal loading on TiO2 and the optimum metal content varies depending on the nature of the metal as mentioned in this paper.
Abstract: The photocatalytic reduction of dinitrogen to ammonia is influenced by the nature and amount of metal loading on TiO2. The optimum metal content varies depending on the nature of the metal. A correlation between the ammonia yield and the intermediary MH bond strength is established (low bond strength gives rise to low ammonia yield).
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TL;DR: The latest achievements in the utilization of plasmons in driving CO2 reduction and N2 fixation into high-value products are comprehensively described and an outlook on the direction and prospects for future work is given.
Abstract: The photochemical production of fuels using sunlight is an innovative way for meeting the quickly increasing energy demands. One of the largest challenges is to develop high-performance photocatalysts that can meet the requirements of practical applications. Owing to their intriguing localized surface plasmon resonances, noble metal nanoparticles and nanostructures show a great potential for enhancing the photocatalytic efficiency and thereby have attracted rapidly growing interest recently. Here, for the first time, the latest achievements in the utilization of plasmons in driving CO2 reduction and N2 fixation into high-value products are comprehensively described. The involved plasmonic enhancement mechanisms in the two types of reactions are fully illustrated. A particular emphasis is given to the outlook on the direction and prospects for future work in this topic.
147 citations
TL;DR: The presented catalysts are superior to the wüstite-based Fe catalyst, which is known as a highly active industrial catalyst at low temperatures and pressures.
Abstract: A low-temperature ammonia synthesis process is required for on-site synthesis. Barium-doped calcium amide (Ba-Ca(NH2 )2 ) enhances the efficacy of ammonia synthesis mediated by Ru and Co by 2 orders of magnitude more than that of a conventional Ru catalyst at temperatures below 300 °C. Furthermore, the presented catalysts are superior to the wustite-based Fe catalyst, which is known as a highly active industrial catalyst at low temperatures and pressures. Nanosized Ru-Ba core-shell structures are self-organized on the Ba-Ca(NH2 )2 support during H2 pretreatment, and the support material is simultaneously converted into a mesoporous structure with a high surface area (>100 m2 g-1 ). These self-organized nanostructures account for the high catalytic performance in low-temperature ammonia synthesis.
143 citations
TL;DR: In this article, a novel ternary metal sulfide photocatalyst Zn0.1Sn0.8S with outstanding nitrogen photofixation ability under visible light was reported.
138 citations
01 Jun 2019
134 citations
TL;DR: In this paper, single Ru decorated TiO2 nanosheets rich in oxygen vacancies were synthesized, which greatly promoted photoreduction of aqueous N2 to NH3, affording an NH3 formation rate of 56.3 μg/h/gcat.
Abstract: Photocatalysis shows a great potential for N2 fixation to NH3 under mild conditions, which intrigues increasing research attention in recent decades. To this end, the design of efficient photocatalysts is the key. Herein, we report the synthesis of single atom Ru decorated TiO2 nanosheets rich in oxygen vacancies. Single Ru sites greatly promoted photoreduction of aqueous N2 to NH3, affording an NH3 formation rate of 56.3 μg/h/gcat. We found that isolated Ru atoms likely weakened the hydrogen evolution, promoted absorption of N2, and also improved the charge carrier separation, which led to enhanced N2 photofixation.
127 citations
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TL;DR: In this paper, the dependence of the exchange current for the electrolytic evolution of hydrogen on metals (i 0,H ) on the work function is analyzed on the basic of a new list of polycrystalline surfaces.
1,474 citations
TL;DR: The photolysis of chemisorbed water on incompletely outgassed TiO/sub 2/ powder yields H 2 and O 2 in the molar ratio of 2 : 1 if conducted under argon in the presence of molecular nitrogen as mentioned in this paper.
Abstract: The photolysis of chemisorbed water on incompletely outgassed TiO/sub 2/ powder yields H/sub 2/ and O/sub 2/ in the molar ratio of 2 : 1 if conducted under argon In the presence of molecular nitrogen, O/sub 2/ is still formed but the evolution of H/sub 2/ is inhibited as chemisorbed nitrogen is reduced to NH/sub 3/ and traces of N/sub 2/H/sub 4/ according to N/sub 2/ + 3H/sub 2/O + nhv yields 2NH/sub 3/ + 150/sub 2/ and N/sub 2/ + 2H/sub 2/O + mhv yields N/sub 2/H/sub 4/ + O/sub 2/ Iron doping enhances the photocatalytic reactivity of rutile and provides prototypes of solar cells for photochemical ammonia synthesis from N/sub 2/ and H/sub 2/O
817 citations
TL;DR: In this article, the improvement of H/sub 2/ evolution from two different types of catalytic p-type photocathode surfaces has been examined, and a comparison of the naked p-Si, the simply platinized, and the (PQ/sup 2 +//sup ///sup +/.)sub n/.nPt(0))/sub surf/ system compared to the same surface directly platinised confirm an important difference in the mechanism of H /sub 2 / evolution catalysis for the two surface catalyst systems.
Abstract: The improvement of H/sub 2/ evolution from two different types of catalytic p-type photocathode surfaces has been examined. p-Type Si has been platinized by phtotelectrochemically plating Pt(0) onto the Si surface. Such a photocathode shows significant improvement (compared to naked p-type Si) for photochemical H/sub 2/ evolution with respect to output photovoltage, fill factor, and overall efficiency. Such photocathodes having an optimun amount of Pt(0) give a pH-dependent output voltage with respect to the H/sub 2/O/H/sub 2/ couple, but the dependence is not a simple 59-mV/pH dependence. No pH dependence would be expected if Pt(0) formed a Schottky barrier when plated onto p-type Si. A second kind of H/sub 2/ evolution catalyst has been confined to the surface of p-type Si. Polymeric quantities of an electroactive N,N'-dialkyl-4,4'-bipridinium reagent, (PQ/sup 2 +/.)/sub n/, have been confined to the surface. The Br/sup -/ counterions of the polymer are then exchanged by PtCl/sub 6//sup 2 -/. Photoreduction then yields Pt(0) dispersed in the polymer. Such a surface is again significantly improved compared to naked p-type Si with respect to H/sub 2/ evolution. A comparison of the naked p-Si, the simply platinized, and the (PQ/sup 2 +//sup ///sup +//sub n/.nPt(0))/sub surf./ system is mademore » and contrasted to the expected behavior of an external Schottky barrier photocell driving an electrolysis cell with a Pt cathode. Experiments with n-type MoS/sub 2/, n-type Si, Pt, Au, and W cathodes functionalized with the (PQ/sup 2 +//sup ///sup +/.)sub n/.nPt(0))/sub surf./ system compared to the same surface directly platinized confirm an important difference in the mechanism of H/sub 2/ evolution catalysis for the two surface catalyst systems. p-Type Si modified with optimum amounts of Pt(0) by direct platinization appears to give improved H/sub 2/ evolution efficiency by a mechanism where the Pt(0) serves as a catalyst that does not alter the interface energetics of the semiconductor.« less
318 citations
TL;DR: The quantum yield of hydrogen production was increased greatly by supporting metals or metal complexes on the TiO2 surface, amounting to 38% for a Pt-TiO2 photocatalyst.
218 citations
TL;DR: In this paper, the Fermi level difference of p-InP and H/sup +//H/sub 2/ (0.9 +/- 0.2 eV) was shown to be a function of metal work functions.
Abstract: Noble metal incorporation in the surface of p-type semiconductor photocathodes to catalyze hydrogen evolution leads to efficient solar to chemical conversion if a set of energetic and kinetic criteria are satisfied: (1) the semiconductor-catalyst junction barrier height must be equal to or greater than that of the semiconductor H/sup +//H/sub 2/ junction; (2) the recombination velocity of photogenerated electrons at the semiconductor-catalyst interface must be low; (3) the overpotential for hydrogen evolution at solar cell current densities (approx.30 mA/cm/sup 2/) must be minor. Because of substantial differences in the vacuum work functions of Pt, Rh, Ru, and the (redox potential of the) H/sup +//H/sub 2/ couple, the barrier heights for junctions of each of the four systems with p-InP ought to vary widely. Yet experiments show that all p-InP(M)/H/sup +//H/sub 2/ junctions, where M = Pt, Rh, Ru, or no metal, have essentially the same approx.0.7-V gain in onset potential for hydrogen evolution relative to Pt/H/sup +//H/sub 2/. We attribute the similarity to the known lowering of metal work functions upon hydrogen alloying. Such alloying increases the barrier height and thereby the gain in onset potential over that anticipated from the vacuum work functions. The barrier height, measured as themore » limiting value of onset potential gain at high irradiance, approaches in all cases the Fermi level difference of p-InP and H/sup +//H/sub 2/ (0.9 +/- 0.2 eV). That Fermi level pinning by interfacial states is not the cause of the similar barriers is evident from the reversible decrease in onset potential with hydrogen depletion and by a unity diode perfection factor of the p-InP(Rh)/H/sup +//H/sub 2/ photocathode, which indicates no measurable interfacial recombination of photogenerated carriers. In agreement, the quantum efficiency of carrier collection (hydrogen evolution) nears unity.« less
184 citations