# Presentation: 187006

## Basic Research Needs 

**Basic Energy Sciences **
**Advisory Committee Meeting**
**Harriet Kung (DOE/BES)**
**harriet.kung@science.doe.gov**
**October 20, 2003**

**Basic Research Needs **
**For the Hydrogen Economy**

## Hydrogen: A National Initiative

**President Bush, State-of the-Union Address,  January 28, 2003**
**  **

***Hydrogen: A National Initiative***

## Drivers for the Hydrogen Economy:

***Drivers for the Hydrogen Economy:***

***  ******Reduce Reliance on Fossil ******	******Fuels  ***
*** ******Reduce Accumulation of ******	******Greenhouse Gases***

## The Hydrogen Economy

**gas or**
**hydride**
**storage**

## Fundamental Issues

***Fundamental Issues***

**The hydrogen economy is a compelling vision:**
- 	- It provides an abundant, clean, secure and flexible energy
-                source
- 	- Its elements have been demonstrated in the laboratory or
-                in prototypes
**However . . . **
-    	- It does not operate as an integrated network
-    	- It is not yet competitive with the fossil fuel economy in
- 	  cost, performance, or reliability
-    	- The most optimistic estimates put the hydrogen economy
-          decades away

## Workshop Chair: 	Millie Dresselhaus 	(MIT)
Associate Chairs:	George Crabtree	(ANL)
		Michelle Buchanan	(ORNL)

**Associate Chairs:****	****George Crabtree****	****(ANL)**
**	****	****Michelle Buchanan****	****(ORNL)**

***Basic Research for Hydrogen Production, ******Storage and Use Workshop, May 13-15, 2003***

**CHARGE:****  To identify fundamental research needs and opportunities in hydrogen production, storage, and use, with a focus on new, emerging and scientifically challenging areas that have the potential to have significant impact in science and technologies.  Highlighted areas will include improved and new materials and processes for hydrogen generation and storage, and for future generations of fuel cells for effective energy conversion. **

**Plenary Session Speakers:**
**	****Steve Chalk **(DOE-EERE) -- overview
**	****George Thomas **(SNL-CA) -- storage
**	****Scott Jorgensen **(GM) -- storage
**	****Jae Edmonds **(PNNL) -- environmental
**	****Jay Keller **(SNL-CA) – hydrogen safety

**Breakout Sessions and Chairs:**
**	****Hydrogen Production **
- 		**Tom Mallouk**, PSU & **Laurie Mets**, U. Chicago
**	****Hydrogen Storage and Distribution*****  ***
- 		**Kathy Taylor**, GM (retired) & **Puru Jena, **VCU
**	****Fuel Cells and Novel Fuel Cell Materials***** ***** **
- 		**Frank DiSalvo**, Cornell & **Tom Zawodzinski**, CWRU

**EERE Pre-Workshop Briefings:**
**	****Hydrogen Storage****	****JoAnn Milliken**** **
**	****Fuel Cells**** ****	****Nancy Garland**
**	****Hydrogen Production****	****Mark Paster**

## Basic Research for Hydrogen Production, Storage and Use Workshop

***Basic Research for Hydrogen Production, ******Storage and Use Workshop***

**125 Participants: **
- Universities
- National Laboratories
- Industries
- DOE: SC and Technology Program Offices
- Other Federal Agencies - including OMB, OSTP, NRL, NIST, NSF, NAS, USDA, and House Science Committee Staffer

**Remarks from News Reporters:**
_***American Institute of Physics Bulletin of Science Policy News Number 71***_
- “Dresselhaus remarked that there were some “very promising” ideas, and she was more optimistic after the workshop that some of the potential showstoppers may have solutions.” “... solving the problems will need long-term support across several Administrations.  Progress will require the cooperation of different offices within DOE, and also the involvement of scientists from other countries, ...”
_***C&E News June 9, 2003***_** **
**“****MOVING TOWARD A HYDROGEN ECONOMY” **DOE Workshop Brings Together Scientists to Prioritize Research Needs for Switching to Hydrogen Economy.

## Workshop Goals

**Research needs and opportunities to address long term “Grand Challenges” and to overcome “show-stoppers.” **
**Prioritized research directions with greatest promise for impact on reaching long-term goals for hydrogen production, storage and use.  **
**Issues cutting across the different research topics/panels that will need multi-directional approaches to ensure that they are properly addressed.  **
**Research needs that bridge basic science and applied technology.**

***Workshop Goals***

**To identify:**

## Hydrogen Production Panel

_**Current status:**_** **
**  ****Steam-reforming of oil and natural gas produces 9M tons H****2****/yr.**
**  ****We will need 40M tons/yr for transportation.**
**  ****Requires CO****2**** sequestration.**
_**Alternative sources and technologies:**_** **
_**Coal:**_**  **
** ****Cheap, lower H****2**** yield/C, more contaminants.**
** ****R&D needed for process development, gas separations, ****	****catalysis, impurity removal.**
_**Solar:**_** **
** ****Widely distributed carbon-neutral; low energy density.**
** ****PV/electrolysis current standard – 15% efficient.**
** ****Requires 0.03% of land area to serve transportation.**
** **
_**Nuclear:**_** Abundant; carbon-neutral; long development cycle.**

_**Panel Chairs:  **_Tom Mallouk (Penn State), Laurie Mets (U of Chicago)

## Priority Research Areas in Hydrogen Production

**For the next decade or more hydrogen will mainly be produced using fossil fuel feedstocks. **
**Development of efficient inexpensive **_**catalysts **_**will be key. **
_**Modeling and simulation**_** will play a significant role.**

***Priority Research Areas in Hydrogen Production***

**Inspired by quantum chemical calculations, Ni surface-alloyed with Au (black) on the left is used to reduce carbon poisoning of catalyst, as verified experimentally on the right.**

## Priority Research Areas in Hydrogen Production

**Power conversion efficiency (10%) needs to be increased by reducing losses.**
**Spectral response needs to be extended into the red.**
**Costs need to be reduced in the production of the transparent anode.**
**Low cost TiO****2**** porous nanostructures allow deep light penetration into dye-sensitized solar cells to increase their efficiency.**
**	**

***Priority Research Areas in Hydrogen Production***

**Photochemical solar cells or Gr****ä****tzel cells use cheap porous TiO****2**** with a huge surface area (see right). Dye additives allow absorption of visible light to better match solar spectrum (left).**

## Priority Research Areas in Hydrogen Production

**Biological systems (plants, microbes) can produce  hydrogen from H****2****O.**
**Nanostructured catalysts can mimic biological systems for H****2 ****production. **
**Biomimetic catalysts may play important roles in future electrochemical and photochemical hydrogen-related processes.**

***Priority Research Areas in Hydrogen Production***

**Synthetic catalysts, such as water oxidation catalysts based on the design of the natural photosynthesis II Mn cluster (upper left) or hydrogen activation catalysts based on the design of the natural reversible Iron-hydrogenase H-cluster (lower right), show promise in mimicking many of the catalytic properties of their natural counterparts. **

## Priority Research Areas in Hydrogen Production

_**Nuclear and Solar Thermal Hydrogen to split H**__**2**__**O**_
**	****Nanostructures may allow the high efficiency achieved in thermo-chemical hydrogen production cycles to occur under less severe environmental conditions.**

***Priority Research Areas in Hydrogen Production***

**Operation at high temperature (500-950 ****o****C) for thermal hydrogen production cycles places severe demands on reactor design and on materials.**
**Use of solar concentrator technology needs to be explored.**
**Efforts to lower operating temperatures offer major challenges for catalyst development.**

## Priority Research Areas in Hydrogen Production

**	****Molecular level understanding of catalytic mechanisms, nanoscale catalyst design, high temperature gas separation**
_**Solar Photoelectrochemistry/Photocatalysis**_
**	****Light harvesting**, **charge transport, chemical assemblies, bandgap engineering, interfacial chemistry, catalysis and photocatalysis, organic semiconductors, theory and modeling, and stability**
_**Bio- and Bio-inspired H**_**2**_** Production**_
**	****Microbes & component redox enzymes, nanostructured 2D & 3D hydrogen/oxygen catalysis, sensing, and energy transduction, engineer robust biological and biomimetic H****2**** production systems**
_**Nuclear and Solar Thermal Hydrogen**_
**	****Thermodynamic data and modeling for thermochemical cycle (TC), high temperature materials: membranes, TC heat exchanger materials, gas separation, improved catalysts**

***Priority Research Areas in Hydrogen Production***

**Dye-Sensitized Solar Cells**

**Ni surface-alloyed with Au to reduce carbon poisoning**

**Synthetic Catalysts for Water Oxidation and Hydrogen Activation**

## Hydrogen Storage Panel

** ****Tanks for gaseous or liquid hydrogen storage. **
** ****Progress demonstrated in solid  state storage materials.**
_**Target Applications**_
** ****Transportation:  on-board vehicles storage.**
** ****Non-transportation: applications for hydrogen production/delivery. **
_**System Requirements**_
** ****Demand compact, light-weight, affordable storage.  **
** ****System requirements set for FreedomCAR: 4.5 wt% for 2005, 9 wt% for 2015. **
** ****No current storage system or material meets all targets. **
**(Currently: Solid Storage ******** 3%; Liquid and Gas Storage ******** 4%)**

***Hydrogen Storage Panel***

_**Panel Chairs:  **_Kathy Taylor (GM, retired), Puru Jena** **(Virginia Commonwealth U)

## High Gravimetric H Density Candidates

***High Gravimetric H Density Candidates***

**Based on Schlapbach and Zuttel, 2001**

**Notes:**
CH4:   25 wt % hydrogen, but inefficient uptake/release
Ideally, should mimic the high wt % of CH4 with fast kinetics of metal hydrides
Light metal hydrides – LiH, ionically bonded
Alanates: M+n (AlH4)-n, M=Li,Na,K,Mg,..
Borohydrides M+n(BH4)–n
Have observed high desorption temperature of alanates may be lowered by adding Ti – WHY?

## Using Neutrons to “See” Hydrogen

**Metal hydrides such as alanates allow high hydrogen volume density, but temperature of hydrogen release also tends to be high.**
**Nanostructured materials may improve absorption volume.**
**Incorporated catalysts may improve release.**

***Using Neutrons to “See” Hydrogen***

**The large neutron cross sections of hydrogen and deuterium make neutrons an ideal probe for in situ studies of hydrogen-based chemical reactions, surface interactions, catalytic reactions and of hydrogen in penetrating through membranes.**

***Priority Research Areas in Hydrogen Storage***

## Carbon Nanotubes for Hydrogen Storage

**A computational representation of hydrogen adsorption in an optimized array of (10,10) nanotubes at 298 K and 200 Bar.  The red spheres represent hydrogen molecules and the blue spheres represent carbon atoms in the nanotubes, showing 3 kinds of binding sites. (K. Johnson et al.)**
**   **

***Carbon Nanotubes for Hydrogen Storage***

**The very small size and very high surface area of carbon nanotubes make them interesting for hydrogen storage. **
**Challenge is to increase the H:C stoichiometry and to strengthen the H—C bonding at 300 K.**

## Priority Research Areas in Hydrogen Storage

**Nanoscale materials have high surface areas, novel shapes, with properties much different from their 3D counterparts – especially useful for catalysts and catalyst supports.**

***Priority Research Areas in Hydrogen Storage***

**Nanostructures such as cup-stacked carbon nanofibers (less than 10nm diameter) and other high surface area structures are being developed to support tiny nanocatalyst particles (2nm) in the regions between the cups. Results obtained thus far are encouraging for specific applications****.**

**Enhanced hydrogen adsorption on high surface area nanostructures may be attained by selective manipulation of surface properties. **
**Nanostructures also have other opportunities for use for hydrogen storage.**

## Priority Research Areas in Hydrogen Storage

_**Theory and Modeling**_
**	****Model systems for benchmarking against calculations at all length scales, integrating disparate time & length scales, first principles methods applicable to condensed phases**

***Priority Research Areas in Hydrogen Storage***

**First principles density functional theory shows that neutral AlH****4 ****dissociates into AlH****2**** + H****2  ****but that ionized AlH****4****-**** tightly binds 4 hydrogens.**
**Calculations further show that Ti substitutes for Na in NaAlH****4**** and weakens the Al-H ionic bond, thus making it possible to dramatically lower the temperature of H****2**** desorption  (by approximately 100****°****C).  **
**(unpublished calculations of **
**P. Jena, co-chair of Hydrogen Storage Panel).**

## Priority Research Areas in Hydrogen Storage

**	****Degradation, thermophysical properties****, effects of surfaces, ****processing, dopants, and catalysts in improving kinetics, nanostructured composites**
_**Nanoscale/Novel Materials**_
**	****Finite size, shape, and curvature effects on electronic states, thermodynamics, and bonding, heterogeneous compositions and structures, catalyzed dissociation and interior storage phase**
** **
_**Theory and Modeling**_
**	****Model systems for benchmarking against calculations at all length scales, integrating disparate time & length scales, first principles methods applicable to condensed phases**

***Priority Research Areas in Hydrogen Storage***

- NaBH4 + 2 H2O             4 H2 + NaBO2

**H Adsorption in Nanotube Array**

**Neutron Imaging of Hydrogen**

**Cup-Stacked Carbon Nanofiber**

**Notes:**
Illustrated above is a schematic for a single-crystal x-ray structure for the metal-organic framework of composition Zn4O(1,4 benzene dicarboxylate)3 showing a single cube fragment of a cubic three-dimensional extended porous structure.  This metal-organic compound adsorbed up to 4.5 wt. % hydrogen at 78 K and 1 wt % at ambient temperature and 20 bar.  Variants of this structure show promise for even better performances regarding hydrogen storage.  [Ref. 16]

## Fuel Cells and Novel Fuel Cell Materials Panel

_**Current status:**_** **
**Engineering investments have been a success. **
**Limits to performance are materials, which have not changed much in 15 years.**

_**Panel Chairs:  **_Frank DiSalvo (Cornell), Tom Zawodzinski (Case Western Reserve)

_**Challenges:**_
**  ****Membranes**
** ****Operation in lower humidity, strength **
**   ****and durability. **
** ****Higher ionic conductivity. **
**  ****Cathodes**** **
**  ****Materials with lower overpotential and resistance to impurities.**
**  ****Low temperature operation needs cheaper (non- Pt) materials.**
**  ****Tolerance to impurities: CO, S, hydrocarbons. **
**  ****Reformers**
**  ****Need low temperature and inexpensive reformer catalysts.**

**2H****2**** + O****2**** ******** 2H****2****O + electrical power + heat**

## Priority Research Areas in Fuel Cells

_**Electrocatalysts and Membranes**_
**	****Oxygen reduction cathodes, minimize rare metal usage in cathodes and anodes, synthesis and processing of designed triple percolation electrodes**
_**Low Temperature Fuel Cells**__** **_
**	****‘****Higher’ temperature proton conducting membranes, degradation mechanisms, functionalizing materials with tailored nano-structures**
_**Solid Oxide Fuel Cells**_
**	****Theory, modeling and simulation, validated by experiment, for electrochemical materials and processes, new materials-all components, novel synthesis routes for optimized architectures, advanced in-situ analytical tools**

***Priority Research Areas in Fuel Cells***

- Source: H. Gasteiger (General Motors)

**Mass of Pt Used in the Fuel Cell **
****** ****a Critical Cost Issue**

**Controlled design of triple percolation nanoscale networks: ions, electrons, and porosity for gases**

**YSZ Electrolyte for SOFCs**

**Porosity can be tailored**

- Source: T. Zawodzinski (CWRU)

- Source: R. Gorte (U. Penn)

**Notes:**
Triple percolation=electrical conduction, ionic conduction, porosity for gases

## High Priority Research Directions 

**Low-cost and efficient solar energy production of hydrogen**
**Nanoscale catalyst design**
**Biological, biomimetic, and bio-inspired materials and processes **
**Complex hydride materials for hydrogen storage**
**Nanostructured / novel hydrogen storage materials**
**Low-cost, highly active, durable cathodes for low-temperature fuel cells**
**Membranes and separations processes for hydrogen production and fuel cells**
**Analytical and measurement technologies**
**Theory, modeling, and simulation **

## •  Catalysis
	- hydrocarbon reforming
	- hydrogen storage kinetics
	- fuel cell and electrolysis electrochemistry  
•  Membranes and Separation
•  Nanoscale Materials and Nanostructured Assemblies 
•  Characterization and Measurement Techniques
•  Theory and Modeling
•  Safety and Environment

**•  ****Catalysis**
**	****- ****hydrocarbon reforming**
**	****- hydrogen storage kinetics**
**	****- fuel cell and electrolysis electrochemistry****  **
**•  ****Membranes and Separation**
**•  ****Nanoscale Materials and Nanostructured Assemblies **
**•  ****Characterization and Measurement Techniques**
**•  ****Theory and Modeling**
**•  ****Safety and Environment**

## Messages

**http://www.sc.doe.gov/bes/**
**hydrogen.pdf**

**Enormous gap between present state-of-the-art capabilities and requirements that will allow hydrogen to be competitive with today’s **
**   ****energy technologies**
**production: 9M tons  ********  40M tons ****(vehicles)**
**storage: 4.4 MJ/L ****(10K psi gas)**** ******** 9.72 MJ/L**
**fuel cells: $3000/kW ****** **$35/kW ****(gasoline engine)**
**Enormous R&D efforts will be required**
**Simple improvements of today’s technologies**
**      ****will not meet requirements**
**Technical barriers can be overcome only with high risk/high payoff basic research**
**Research is highly interdisciplinary, requiring chemistry, materials science, physics, biology, engineering, nanoscience, computational science**
**Basic and applied research should couple seamlessly**

## DOE
Hydrogen Program Management Plan- EERE, FE, NE, SC
EERE Grand Challenge Solicitation on Hydrogen Storage (~ $150 M for 5 years)

OSTP Hydrogen R & D Task Force Group 
DOC, DOD, DOE, DOT, DOS, CIA, EPA, NASA, NIST, NSF, USDA
Develop Taxonomy of Research Directions to Facilitate Inter-Agency Coordination

IPHE (International Partnership for the Hydrogen Economy)
IPHE Ministerial Meeting and Hydrogen Economy Dialogue, November 2003
To Organize, Evaluate and Coordinate Multinational Research, Development and Deployment Programs 

DOE/European Commission
Implementing Agreement on Hydrogen Research and Applications
Topics include: Hydrogen Production, Carbon Sequestration, Storage, Delivery, Fuel Cells, Codes and Standards, Economic/Cost Modeling

IEA Hydrogen Coordination Group
Hydrogen & Fuel Cells Technology and Policy Programs in IEA Member Countries

**DOE**
**Hydrogen Program Management Plan- EERE, FE, NE, SC**
**EERE Grand Challenge Solicitation on Hydrogen Storage (~ $150 M for 5 years)**
**      **
**OSTP Hydrogen R & D Task Force Group **
**DOC, DOD, DOE, DOT, DOS, CIA, EPA, NASA, NIST, NSF, USDA**
**Develop Taxonomy of Research Directions to Facilitate Inter-Agency Coordination**
**IPHE (International Partnership for the Hydrogen Economy)**
**IPHE Ministerial Meeting and Hydrogen Economy Dialogue, November 2003**
**To Organize, Evaluate and Coordinate Multinational Research, Development and Deployment Programs **
**DOE/European Commission**
**Implementing Agreement on Hydrogen Research and Applications**
**Topics include: Hydrogen Production, Carbon Sequestration, Storage, Delivery, Fuel Cells, Codes and Standards, Economic/Cost Modeling**
**IEA Hydrogen Coordination Group**
**Hydrogen & Fuel Cells Technology and Policy Programs in IEA Member Countries**

## Outreach

**OMB/OSTP Briefing  / SC Briefing**
**March APS**
**DCMP Invited Symposium- Dresselhaus, Norskov, **
**     ****Gasteiger, Gust, Gratzel**
**Wednesday evening plenary?  Energy Secy Abraham invited**
**MRS, ACS will have symposia**
**Council for Chemical Research**
**Physics Today- article by Dresselhaus, Buchanan, Crabtree**
**Nova-  consultants are Nate Lewis, Millie Dresselhaus**
**Jim Lehrer Newshour**
**Interviews by Brazil Major TV Talk Show / Newspaper**