United States

A series of molecular rotors was designed to study and measure the rate accelerating effects of an intramolecular hydrogen bond. The rotors form a weak neutral O–H⋯O[double bond length as m-dash]C hydrogen bond in the planar transition state (TS) of the bond rotation process. The rotational barrier of the hydrogen bonding rotors was dramatically lower (9.9 kcal mol⁻¹) than control rotors which could not form hydrogen bonds. The magnitude of the stabilization was significantly larger than predicted based on the independently measured strength of a similar O–H⋯O[double bond length as m-dash]C hydrogen bond (1.5 kcal mol⁻¹). The origins of the large transition state stabilization were studied via experimental substituent effect and computational perturbation analyses. Energy decomposition analysis of the hydrogen bonding interaction revealed a significant reduction in the repulsive component of the hydrogen bonding interaction. The rigid framework of the molecular rotors positions and preorganizes the interacting groups in the transition state. This study demonstrates that with proper design a single hydrogen bond can lead to a TS stabilization that is greater than the intrinsic interaction energy which has applications in catalyst design and in the study of enzyme mechanisms.

Envisioned below is an energy system named Thermal Hydrogen developed to enable economy-wide decarbonization. Thermal Hydrogen is an energy system where electric and/or heat energy is used to split water (or CO₂) for the utilization of both by-products: hydrogen as energy storage and pure oxygen as carbon abatement. Important advantages of chemical energy carriers are long term energy storage and extended range for electric vehicles. These minimize the need for the most capital intensive assets of a fully decarbonized energy economy: low carbon power plants and batteries. The pure oxygen pre-empts the gas separation process of “Carbon Capture and Sequestration” (CCS) and enables hydrocarbons to use simpler more efficient thermodynamic cycles. Thus the “externality” of water splitting pure oxygen is increasingly competitive hydrocarbons which happen to be emissions free. Methods for engineering economy-wide decarbonization are described below as well as the energy supply carrier and distribution options offered by the system.

Clean energy and fuel storage is often required for both stationary and automotive applications. Some of the clean energy and fuel storage technologies currently under extensive research and development are hydrogen storage direct electric storage mechanical energy storage solar-thermal energy storage electrochemical (batteries and supercapacitors) and thermochemical storage. The gravimetric and volumetric storage capacity energy storage density power output operating temperature and pressure cycle life recyclability and cost of clean energy or fuel storage are some of the factors that govern efficient energy and fuel storage technologies for potential deployment in energy harvesting (solar and wind farms) stations and on-board vehicular transportation. This Special Issue thus serves the need to promote exploratory research and development on clean energy and fuel storage technologies while addressing their challenges to a practical and sustainable infrastructure.

This paper summarises the results from a blind-prediction study for models developed for estimating the consequences of vented hydrogen deflagrations. The work is part of the project Improving hydrogen safety for energy applications through pre-normative research on vented deflagrations (HySEA). The scenarios selected for the blind-prediction entailed vented explosions with homogeneous hydrogen-air mixtures in a 20-foot ISO container. The test program included two configurations and six experiments i.e. three repeated tests for each scenario. The comparison between experimental results and model predictions reveals reasonable agreement for some of the models and significant discrepancies for others. It is foreseen that the first blind-prediction study in the HySEA project will motivate developers to improve their models and to update guidelines for users of the models.

Although hydrogen has been used in industry for decades its use as a fuel for vehicles or stationary power generation in consumer environments is relatively new. As such hydrogen and fuel cell codes and standards are in various stages of development. Industry manufacturers the government and other safety experts are working with codes and standards development organizations to prepare review and promulgate technically-sound codes and standards for hydrogen and fuel cell technologies and systems.



Codes and standards are being adopted revised or developed for vehicles; fuel delivery and storage; fueling service and parking facilities; and vehicle fueling interfaces. Codes and standards are also being adopted revised or developed for stationary and portable fuel cells and interfaces as well as hydrogen generators.  A list of current of international codes and standards is available on the Fuel Cells Codes and Standards Resource.



Link to website

Hydrogen is seen as the future automobile energy storage media due to its inherent cleanliness upon oxidation and its ready utilization in fuel cell applications. Its physical storage in light weight low volume systems is a key technical requirement. In searching for ever higher gravimetric and volumetric density hydrogen storage materials and systems it is inevitable that higher energy density materials will be studied and used. To make safe and commercially acceptable systems it is important to understand quantitatively the risks involved in using and handling these materials and to develop appropriate risk mitigation strategies to handle unforeseen accidental events. To evaluate these materials and systems an IPHE sanctioned program was initiated in 2006 partnering laboratories from Europe North America and Japan. The objective of this international program is to understanding the physical risks involved in synthesis handling and utilization of solid state hydrogen storage materials and to develop methods to mitigate these risks. This understanding will support ultimate acceptance of commercially high density hydrogen storage system designs. An overview of the approaches to be taken to achieve this objective will be given. Initial experimental results will be presented on environmental exposure of NaAlH4 a candidate high density hydrogen storage compound. The tests to be shown are based on United Nations recommendations for the transport of hazardous materials and include air and water exposure of the hydride at three hydrogen charge levels in various physical configurations. Additional tests developed by the American Society for Testing and Materials were used to quantify the dust cloud ignition characteristics of this material which may result from accidental high energy impacts and system breach. Results of these tests are shown along with necessary risk mitigation techniques used in the synthesis and fabrication of a prototype hydrogen storage system.

In close cooperation with their Canadian counterparts United States public safety authorities are taking the first steps towards creating a proper infrastructure to ensure the safe use of the new hydrogen fuel cells now being introduced commercially. Currently public safety officials are being asked to permit hydrogen fuel cells for stationary power and as emergency power backups for the telecommunications towers that exist everywhere. Consistent application of the safety codes is difficult – in part because it is new – yet it is far more complex to train emergency responders to deal safely with the inevitable hydrogen incidents. The US and Canadian building and fire codes and standards are similar but not identical. The US and Canadian rules are unlikely to be useful to other nations without modification to suit different regulatory systems. However emergency responder safety training is potentially more universal. The risks strategies and tactics are unlikely to differ much by region. The Hydrogen Executive Leadership Panel (HELP) made emergency responder safety training its first priority because the transition to hydrogen depends on keeping incidents small and inoffensive and the public and responders safe from harm. One might think that advising 1.2 million firefighters and 800000 law enforcement officers about hydrogen risks is no more complicated than adding guidance to a website. One would be wrong. The term “training” has specific legal implications which may vary by state. For hazardous materials federal requirements apply. Insurance companies place training requirements on the policies they sell to fire departments including the thousands of small all-volunteer departments which may operate as private corporations. Union contracts may define training and promotions may be based on satisfactorily completed certain levels of training. Emergency responders could no sooner learn how to extinguish a<br/>hydrogen fire by reading a webpage than a person could learn to ride a bicycle by reading a book. Procedures must be learned by listening reading and then doing. Regular practice is necessary. As new hydrogen applications are commercialized additional responder training may be necessary. This highlights another obstacle emergency responders’ ability to travel distances and take the time to undergo training. Historically fire academies established adjunct instructor programs and satellite academies to bring the training to firefighters. The large well-equipped academies are typically used for specialized training. States rarely have enough instructors and instructors often must take the time to create a course outline research each point and produce a program that is informative useful and holds the attention of responders. The challenge of training emergency responders seems next to impossible but public safety authorities are asked to tackle the impossible every day and a model exists to move forward in the U.S. Over the past few years the National Association of State Fire Marshals and U.S. Department of Transportation enlisted the help of emergency responders and industry to create a standardized approach to train emergency responders to deal with pipeline incidents. A curriculum and training materials were created and more than 26000 sets have been distributed for free to public safety agencies nationwide. More than 8000 instructors have been trained to use these materials that are now part of the regular training in 23 states. Using this model HELP intends to ensure that all emergency responders are trained to address hydrogen risks. The model and the rigorous scenario analysis and review used to developing the operational and technical training is addressed in this paper.

The permitting process for hydrogen fueling stations varies from country to country. However a common step in the permitting process is the demonstration that the proposed fueling station meets certain safety requirements. Currently many permitting authorities rely on compliance with well known codes and standards as a means to permit a facility. Current codes and standards for hydrogen facilities require certain safety features specify equipment made of material suitable for hydrogen environment and include separation or safety distances. Thus compliance with the code and standard requirements is widely accepted as evidence of a safe design. However to ensure that a hydrogen facility is indeed safe the code and standard requirements should be identified using a risk-informed process that utilizes an acceptable level of risk. When compliance with one or more code or standard requirements is not possible an evaluation of the risk associated with the exemptions to the requirements should be understood and conveyed to the Authority Having Jurisdiction (AHJ). Establishment of a consistent risk assessment toolset and associated data is essential to performing these risk evaluations. This paper describes an approach for risk-informing the permitting process for hydrogen fueling stations that relies primarily on the establishment of risk-informed codes and standards. The proposed risk-informed process begins with the establishment of acceptable risk criteria associated with the operation of hydrogen fueling stations. Using accepted Quantitative Risk Assessment (QRA) techniques and the established risk criteria the minimum code and standard requirements necessary to ensure the safe operation of hydrogen facilities can be identified. Risk informed permitting processes exist in some countries and are being developed in others. To facilitate consistent risk-informed approaches the participants in the International Energy Agency (IEA) Task 19 on hydrogen safety are working to identify acceptable risk criteria QRA models and supporting data.

Experience makes a superior teacher. Sharing the details surrounding safety events is one of the best ways to help prevent their recurrence elsewhere. This approach requires an open non-punitive environment to achieve broad benefits. The Hydrogen Incident Reporting Tool (www.h2incidents.org) is intended to facilitate the sharing of lessons learned and other relevant information gained from actual experiences using and working with hydrogen and hydrogen systems. Its intended audience includes those involved in virtually any aspect of hydrogen technology systems and use with an emphasis towards energy and transportation applications. The database contains records of safety events both publicly available and/or voluntarily submitted. Typical records contain a general description of the occurrence contributing factors equipment involved and some detailing of consequences and changes that have been subsequently implemented to prevent recurrence of similar events in the future. The voluntary and confidential nature and other characteristics surrounding the database mean that any analysis of apparent trends in its contents cannot be considered statistically valid for a universal population. A large portion of reported incidents have occurred in a laboratory setting due to the typical background of the reporting projects for example. Yet some interesting trends are becoming apparent even at this early stage of the database’s existence and general lessons can already be taken away from these experiences. This paper discusses the database and a few trends that have already become apparent for the reported incidents. Anticipated future uses of this information are also described. This paper is intended to encourage wider participation and usage of the incidents reporting database and to promote the safety benefits offered by its contents.

The Hydrogen Safety Codes and Standards program element of the US Department of Energy's Fuel Cell Technologies Office provides coordination and technical data for the development of domestic and international codes and standards related to hydrogen technologies. The materials compatibility program task at Sandia National Laboratories (Livermore CA) is focused on developing the technical basis for qualifying materials for hydrogen service i.e. accommodating hydrogen embrittlement. This presentation summarizes code development activities for qualifying materials for hydrogen service with emphasis on the scientific basis for the testing methodologies including fracture mechanics based measurements (fracture threshold and fatigue crack growth) total fatigue life measurements and full- scale pressure vessel testing.