Formic acid (HCOOH), with a hydrogen capacity of 4.3 wt. %, has attracted increasing interest in the utilization as a promising H 2 carrier. The CO 2 -HCOOH cycle is believed to be a simple and environmental-friendly process for the charge and discharge of H 2 . In this review, we summarize the state-of-the-art technologies and recent results of the heterogeneously catalyzed dehydrogenation of formic acid. Based on these achievements, future outlooks for improving this system for practical applications are proposed.

IL-1 receptor antagonist (IL-1ra) is a cytokine that competitively binds the IL-1 receptor to antagonize IL-1 activity without any agonist function. Previous experiments indicated that the ratio of IL-1ra to IL-1alpha in the normal stratum corneum (SC) was much higher in the sun-exposed face than in the sun-protected area, upper arms. It was also reported by another laboratory that IL-1ra is increased in the lesional skin of psoriatic patients. This study was designed to measure the contents of IL-1alpha and IL-1ra in non-lesional and pathological SC obtained from inflammatory skin diseases including psoriasis and non-psoriatic dermatoses such as atopic dermatitis. The SC materials were obtained with a non-invasive tape-stripping method. Their soluble fractions were prepared and assayed for IL-1alpha and IL-1ra by enzyme-linked immunosorbent assays. As a result we confirmed the previous findings that the ratio of IL-1ra to IL-1alpha in the normal SC was much higher in the face than in the sun-protected sites, the trunk as well as extremities. Next, we found that IL-1alpha contents were significantly reduced in the SC samples obtained from inflammatory skin regardless of whether their IL-1ra contents increased or unchanged. Moreover, we noted that an increased ratio of IL-1ra to IL-1alpha in the SC was not specific to psoriasis, but was also found in other inflammatory skin diseases including atopic dermatitis. This ratio was found to become lower after successful treatment of these skin lesions with topical glucocorticoids. We conclude from these observations that the increased ratio of IL-1ra to IL-1alpha in the SC is a non-specific phenomenon that can occur in any inflammatory skin diseases regardless of the inflammatory pattern, probably reflecting a skin regulation process against various kinds of inflammation.

Patients with hydroa vacciniforme (HV)-like eruptions and malignant potential have been reported from Asia and Mexico, and those patients frequently had an associated latent Epstein-Barr virus (EBV) infection. In order to elucidate the association of latent EBV infection with HV, we studied six children with typical manifestations of HV by detection of EBV genes and EBV-related RNAs in biopsy specimens from cutaneous lesions. Cutaneous lesions of all six children with typical HV contained EBV-encoded small nuclear RNA (EBER)+ cells in 3-10% of the dermal infiltrates, whereas no Bam HI-H, l-fragment (BHLF) mRNA, or transcripts encoding EA-D antigen, were detected. No EBER + cells were detected in other inflammatory or benign lymphoproliferative skin disorders tested. Polymerase chain reaction amplification confirmed the presence of EBV DNA sequences in five of six biopsy specimens from the patients. Latent EBV infection is associated with the development of cutaneous lesions of HV.

We report a ruthenium complex containing an N,N'-diimine ligand for the selective decomposition of formic acid to H and CO in water in the absence of any organic additives. A turnover frequency of 12 000 h and a turnover number of 350 000 at 90 °C were achieved in the HCOOH/HCOONa aqueous solution. Efficient production of high-pressure H and CO (24.0 MPa (3480 psi)) was achieved through the decomposition of formic acid with no formation of CO. Mechanistic studies by NMR and DFT calculations indicate that there may be two competitive pathways for the key hydride transfer rate-determining step in the catalytic process.

We are engaged in research and development to reduce CO 2 emissions. Longterm increase of CO 2 concentration in the atmosphere has a great influence on climate change. [1] Therefore, developing technologies aiming to reduce CO 2 emissions and to overcome the present society depending on fossil fuels as primary energy. Additionally, transition of fossil fuels into renewable energies is also important for realizing future sustainable society. [2] The most suitable material for this goal is considered to be hydrogen, because its combustion emits only water as a byproduct. In addition, hydrogen possesses almost three times as much energy as natural gases, and can supply electric power very efficiently for fuel cells without releasing greenhouse gases and air pollutants. [3] However, hydrogen also has serious drawbacks for practical applications. Most serious problem is that, hydrogen forms as a gas at ambient conditions with very low density (0.0899 kg m −3 at 0 °C, 0.10 MPa) over ten times lower than air (1.293 kg m −3 at 0 °C, 0.10 MPa). As a result, it becomes difficult to store and transport hydrogen safely. Developing safe and efficient hydrogen storage materials is one of the most difficult challenges for the transformation from the fossil fuel-based economy to hydrogen-based one as a long-term solution for a safe energy future.Hydrogen has attracted considerable attention as an energy source, and various attempts to develop suitable methods for hydrogen generation are made at the National Institute of Advanced Industrial Science and Technology. In this paper, the authors introduce their recent strategies to store hydrogen using formic acid (FA) as a hydrogen carrier. FA, which is believed to be one of the most promising liquid organic hydrogen carriers, can provide a viable method for safe hydrogen transportation. In order to optimize the performance of hydrogen storage with FA, the authors have investigated both homogeneous and heterogeneous catalysts. For example, Ir catalysts anchoring N^N-bidentate ligands show high catalytic activity for both the reactions of FA synthesis and hydrogen generation from FA. Ultrafine Pd-based nanoparticles are also immobilized on various supports, which show excellent catalytic performance for FA dehydrogenation under mild conditions. The authors also develop both homogeneous and heterogeneous catalysts to generate high-pressure gases (H 2 and CO 2 ) over 120 and 35 MPa, respectively,

Carbon dioxide may constitute a source of chemicals and fuels if efficient and renewable processes are developed that directly utilize it as feedstock. Two of its reduction products are formic acid and methanol, which have also been proposed as liquid organic chemical carriers in sustainable hydrogen storage. Here we report that both the hydrogenation of carbon dioxide to formic acid and the disproportionation of formic acid into methanol can be realized at ambient temperature and in aqueous, acidic solution, with an iridium catalyst. The formic acid yield is maximized in water without additives, while acidification results in complete (98 %) and selective (96 %) formic acid disproportionation into methanol. These promising features in combination with the low reaction temperatures and the absence of organic solvents and additives are relevant for a sustainable hydrogen/methanol economy.

Atmospheric densities and viscosities of ionic l i q u i d s , 1 -h e x y l -3 -m e t h y l i m i d a z o l i u m b i s -were measured with a Stabinger viscometer at temperatures from (293 to 373) K. High-pressure densities (p ≤ 200 MPa) for [C 6 C 1 Im][Tf 2 N] and [C 6 C 1 Im][Cl] were measured with a bellows type apparatus at temperatures from (312 to 452) K. Samples were analyzed for the water and 1-methylimidazole content before and after the measurements. For [C 6 C 1 Im]-[Tf 2 N], combined expanded uncertainties were estimated to be (1.0 and 1.8) kg•m −3 for atmospheric and high-pressure density, respectively, and 0.85 % for viscosity. For [C 6 C 1 Im][Cl], combined expanded uncertainties were estimated to be (1.1 and 2.5) kg•m −3 for atmospheric and high-pressure density, respectively, and 1.59 % for viscosity. The measured densities and viscosities of [C 6 C 1 Im][Tf 2 N] in this work agreed with some of the available literature values within their experimental uncertainties. The effect of colored impurities and the source of sample on densities and viscosities of [C 6 C 1 Im][Cl] were determined to be less than the experimental uncertainties. The [C 6 C 1 Im][Tf 2 N] did not decompose over the full temperature range during the measurements, while [C 6 C 1 Im][Cl] decomposed at temperatures greater than 392 K.

A simple and continuous high‐pressure (>120 MPa) hydrogen production system was developed by the selective decomposition of formic acid at 80 °C using an iridium complex as a catalyst, with a view to its application in future hydrogen fuel filling stations. The system is devoid of any compressing system. The described method can provide high‐pressure H2 with 85 % purity after applying an effective gas–liquid separation process to separate the generated gas obtained from the decomposition of formic acid (H2/CO2=1:1). The efficiency of the catalyst lies with its high turnover frequency (1800 h−1 at 40 MPa) to produce high‐pressure H2 with a good lifetime of >40 h. Interestingly, only very low levels carbon monoxide (less than 6 vol ppm) were detected in the generated gas, even at 120 MPa.